ALBERT

All Library Books, journals and Electronic Records Telegrafenberg

Your email was sent successfully. Check your inbox.

An error occurred while sending the email. Please try again.

Proceed reservation?

Export
Filter
  • American Institute of Physics (AIP)  (49,884)
  • Copernicus
  • International Union of Crystallography (IUCr)
  • 2020-2022  (5,827)
  • 1995-1999  (60,762)
Collection
Publisher
Years
Year
  • 1
    Publication Date: 2020-09-07
    Description: This study presents and discusses horizontal and vertical geodetic velocities for a low strain rate region of the south Alpine thrust front in northeastern Italy obtained by integrating GPS, interferometric synthetic aperture radar (InSAR) and leveling data. The area is characterized by the presence of subparallel, south-verging thrusts whose seismogenic potential is still poorly known. Horizontal GPS velocities show that this sector of the eastern Southern Alps is undergoing ∼1 mm a−1 of NW–SE shortening associated with the Adria–Eurasia plate convergence, but the horizontal GPS velocity gradient across the mountain front provides limited constraints on the geometry and slip rate of the several subparallel thrusts. In terms of vertical velocities, the three geodetic methods provide consistent results showing a positive velocity gradient, of ∼ 1.5 mm a−1, across the mountain front, which can hardly be explained solely by isostatic processes. We developed an interseismic dislocation model whose geometry is constrained by available subsurface geological reconstructions and instrumental seismicity. While a fraction of the measured uplift can be attributed to glacial and erosional isostatic processes, our results suggest that interseismic strain accumulation at the Montello and the Bassano–Valdobbiadene thrusts it significantly contributing to the measured uplift. The seismogenic potential of the Montello thrust turns out to be smaller than that of the Bassano–Valdobbiadene fault, whose estimated parameters (locking depth equals 9.1 km and slip rate equals 2.1 mm a−1) indicate a structure capable of potentially generating a Mw〉6.5 earthquake. These results demonstrate the importance of precise vertical ground velocity data for modeling interseismic strain accumulation in slowly deforming regions where seismological and geomorphological evidence of active tectonics is often scarce or not conclusive.
    Description: Published
    Description: 1681–1698
    Description: 2T. Deformazione crostale attiva
    Description: JCR Journal
    Keywords: Southern Alps ; Vertical Velocities ; GPS and InSAR integration ; Interseismic Deformation ; Dislocation Model ; Seismic Potential ; 04.03. Geodesy ; 04.07. Tectonophysics
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 2
    Publication Date: 2021-06-07
    Description: The diagnosis of the conservation state of monumental structures from constraints to the spatial distribution of their physical properties on shallow and inner materials represents one of the key objectives in the application of non-invasive techniques. In situ, CRP and 3D ultrasonic tomography can provide an effective coverage of stone materials in space and time. The intrinsic characteristics of the materials that make up a monumental structure and affect the two properties (i.e., reflectivity, longitudinal velocity) through the above methods substantially differ. Consequently, the content of their information is mainly complementary rather than redundant. In this study we present the integrated application of different non-destructive techniques i.e., Close Range Photogrammetry (CRP), and low frequency (24 KHz) ultrasonic tomography complemented by petrographycal analysis based essentially on Optical Microscopy (OM). This integrated methodology has been applied to a Carrara marble column of the Basilica of San Saturnino, in Byzantine-Proto-Romanesque style, which is part of the Paleo Christian complex of the V-VI century. This complex also includes the adjacent Christian necropolis in the square of San Cosimo in the city of Cagliari, Sardinia, Italy. The column under study is made of bare material dating back probably to the first century A.D., it was subjected to various traumas due to disassembly and transport to the site, including damage caused by the close blast of a WWII fragmentation bomb. High resolution 3D modelling of the studied artifact was computed starting from the integration of proximal sensing techniques such as CRP based on Structure from Motion (SfM), with which information about the geometrical anomalies and reflectivity of the investigated marble column surface was obtained. On the other hand, the inner parts of the studied body were successfully inspected in a non-invasive way by computing the velocity pattern of the ultrasonic signal through the investigated materials using 3D ultrasonic tomography. This technique gives information on the elastic properties of the material related with mechanical properties and a number of factors, such as presence of fractures, voids, and flaws. Extracting information on such factors from the elastic wave velocity using 3D tomography provides a non-invasive approach to analyse the property changes of the inner material of the ancient column. The integrated application of in situ CRP and ultrasonic techniques provides a full 3D high resolution model of the investigated artifact. This model enhanced by the knowledge of the petrographic characteristics of the materials, improves the diagnostic process and affords reliable information on the state of conservation of the materials used in the construction processes of the studied monumental structure. The integrated use of the non-destructive techniques described above also provides suitable data for a possible restoration and future preservation.
    Description: Copernicus
    Description: Published
    Description: On line
    Description: 5T. Sismologia, geofisica e geologia per l'ingegneria sismica
    Keywords: Cultural Heritage ; Monumental Structures ; Non-Destructive Testing ; Close Range Photogrammetry ; 3D Ultrasonic Tomography ; High resolution 3D modelling ; Restoration ; Conservation ; 05.04. Instrumentation and techniques of general interest
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: Abstract
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 3
    Publication Date: 2020-08-10
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev , info:eu-repo/semantics/article
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 4
    Publication Date: 2021-02-16
    Description: A range of future climate scenarios are projected for high atmospheric CO2 concentrations, given uncertainties over future human actions as well as potential environmental and climatic feedbacks. The geological record offers an opportunity to understand climate system response to a range of forcings and feedbacks which operate over multiple temporal and spatial scales. Here, we examine a single interglacial during the late Pliocene (KM5c, ca. 3.205±0.01 Ma) when atmospheric CO2 exceeded pre-industrial concentrations, but were similar to today and to the lowest emission scenarios for this century. As orbital forcing and continental configurations were almost identical to today, we are able to focus on equilibrium climate system response to modern and near-future CO2. Using proxy data from 32 sites, we demonstrate that global mean sea-surface temperatures were warmer than pre-industrial values, by ∼2.3°C for the combined proxy data (foraminifera Mg∕Ca and alkenones), or by ∼3.2–3.4°C (alkenones only). Compared to the pre-industrial period, reduced meridional gradients and enhanced warming in the North Atlantic are consistently reconstructed. There is broad agreement between data and models at the global scale, with regional differences reflecting ocean circulation and/or proxy signals. An uneven distribution of proxy data in time and space does, however, add uncertainty to our anomaly calculations. The reconstructed global mean sea-surface temperature anomaly for KM5c is warmer than all but three of the PlioMIP2 model outputs, and the reconstructed North Atlantic data tend to align with the warmest KM5c model values. Our results demonstrate that even under low-CO2 emission scenarios, surface ocean warming may be expected to exceed model projections and will be accentuated in the higher latitudes.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 5
    Publication Date: 2020-09-28
    Description: Reconstructions of global hydroclimate during the Common Era (CE; the past ∼2000 years) are important for providing context for current and future global environmental change. Stable isotope ratios in water are quantitative indicators of hydroclimate on regional to global scales, and these signals are encoded in a wide range of natural geologic archives. Here we present the Iso2k database, a global compilation of previously published datasets from a variety of natural archives that record the stable oxygen (δ18O) or hydrogen (δ2H) isotopic compositions of environmental waters, which reflect hydroclimate changes over the CE. The Iso2k database contains 759 isotope records from the terrestrial and marine realms, including glacier and ground ice (210); speleothems (68); corals, sclerosponges, and mollusks (143); wood (81); lake sediments and other terrestrial sediments (e.g., loess) (158); and marine sediments (99). Individual datasets have temporal resolutions ranging from sub-annual to centennial and include chronological data where available. A fundamental feature of the database is its comprehensive metadata, which will assist both experts and nonexperts in the interpretation of each record and in data synthesis. Key metadata fields have standardized vocabularies to facilitate comparisons across diverse archives and with climate-model-simulated fields. This is the first global-scale collection of water isotope proxy records from multiple types of geological and biological archives. It is suitable for evaluating hydroclimate processes through time and space using large-scale synthesis, model–data intercomparison and (paleo)data assimilation. The Iso2k database is available for download at https://doi.org/10.25921/57j8-vs18 (Konecky and McKay, 2020) and is also accessible via the NOAA/WDS Paleo Data landing page: https://www.ncdc.noaa.gov/paleo/study/29593 (last access: 30 July 2020).
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 6
    Publication Date: 2021-07-23
    Description: Originating from the boreal forest and often transported over large distances, driftwood characterises many Arctic coastlines. Here we present a combined assessment of radiocarbon (14C) and dendrochronological (ring width) age estimates of driftwood samples to constrain the progradation of two Holocene beach-ridge systems near the Lena Delta in the Siberian Arctic (Laptev Sea). Our data show that the 14C ages obtained on syndepositional driftwood from beach deposits yield surprisingly coherent chronologies for the coastal evolution of the field sites. The dendrochronological analysis of wood from modern driftlines revealed the origin and recent delivery of the wood from the Lena River catchments. This finding suggests that the duration transport lies within the uncertainty of state-of-the-art 14C dating and thus substantiates the validity of age indication obtained from driftwood. This observation will help to better understand changes in similar coastal environments, and to improve our knowledge about the response of coastal systems to past climate and sea-level changes.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 7
    Publication Date: 2020-11-16
    Description: The Northeast Greenland Ice Stream (NEGIS) extends around 600 km upstream from the coast to its onset near the ice divide in interior Greenland. Several maps of surface velocity and topography of interior Greenland exist, but their accuracy is not well constrained by in situ observations. Here we present the results from a GPS mapping of surface velocity in an area located approximately 150 km from the ice divide near the East Greenland Ice-core Project (EastGRIP) deep-drilling site. A GPS strain net consisting of 63 poles was established and observed over the years 2015–2019. The strain net covers an area of 35 km by 40 km, including both shear margins. The ice flows with a uniform surface speed of approximately 55 m a^−1 within a central flow band with longitudinal and transverse strain rates on the order of 10−4 a^−1 and increasing by an order of magnitude in the shear margins. We compare the GPS results to the Arctic Digital Elevation Model and a list of satellite-derived surface velocity products in order to evaluate these products. For each velocity product, we determine the bias in and precision of the velocity compared to the GPS observations, as well as the smoothing of the velocity products needed to obtain optimal precision. The best products have a bias and a precision of ∼0.5 m a^−1. We combine the GPS results with satellite-derived products and show that organized patterns in flow and topography emerge in NEGIS when the surface velocity exceeds approximately 55 m a−1 and are related to bedrock topography.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev , info:eu-repo/semantics/article
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 8
    facet.materialart.
    Unknown
    Copernicus
    In:  EPIC3Climate of the Past, Copernicus, 16(6), pp. 2275-2323, ISSN: 1814-9332
    Publication Date: 2021-07-01
    Description: We present the Alfred Wegener Institute's contribution to the Pliocene Model Intercomparison Project Phase 2 (PlioMIP2) wherein we employ the Community Earth System Models (COSMOS) that include a dynamic vegetation scheme. This work builds on our contribution to Phase 1 of the Pliocene Model Intercomparison Project (PlioMIP1) wherein we employed the same model without dynamic vegetation. Our input to the PlioMIP2 special issue of Climate of the Past is twofold. In an accompanying paper we compare results derived with COSMOS in the framework of PlioMIP2 and PlioMIP1. With this paper we present details of our contribution with COSMOS to PlioMIP2. We provide a description of the model and of methods employed to transfer reconstructed mid-Pliocene geography, as provided by the Pliocene Reconstruction and Synoptic Mapping Initiative Phase 4 (PRISM4), to model boundary conditions. We describe the spin-up procedure for creating the COSMOS PlioMIP2 simulation ensemble and present large-scale climate patterns of the COSMOS PlioMIP2 mid-Pliocene core simulation. Furthermore, we quantify the contribution of individual components of PRISM4 boundary conditions to characteristics of simulated mid-Pliocene climate and discuss implications for anthropogenic warming. When exposed to PRISM4 boundary conditions, COSMOS provides insight into a mid-Pliocene climate that is characterised by increased rainfall (+0.17 mm d−1) and elevated surface temperature (+3.37 ∘C) in comparison to the pre-industrial (PI). About two-thirds of the mid-Pliocene core temperature anomaly can be directly attributed to carbon dioxide that is elevated with respect to PI. The contribution of topography and ice sheets to mid-Pliocene warmth is much smaller in contrast – about one-quarter and one-eighth, respectively, and nonlinearities are negligible. The simulated mid-Pliocene climate comprises pronounced polar amplification, a reduced meridional temperature gradient, a northwards-shifted tropical rain belt, an Arctic Ocean that is nearly free of sea ice during boreal summer, and muted seasonality at Northern Hemisphere high latitudes. Simulated mid-Pliocene precipitation patterns are defined by both carbon dioxide and PRISM4 paleogeography. Our COSMOS simulations confirm long-standing characteristics of the mid-Pliocene Earth system, among these increased meridional volume transport in the Atlantic Ocean, an extended and intensified equatorial warm pool, and pronounced poleward expansion of vegetation cover. By means of a comparison of our results to a reconstruction of the sea surface temperature (SST) of the mid-Pliocene we find that COSMOS reproduces reconstructed SST best if exposed to a carbon dioxide concentration of 400 ppmv. In the Atlantic to Arctic Ocean the simulated mid-Pliocene core climate state is too cold in comparison to the SST reconstruction. The discord can be mitigated to some extent by increasing carbon dioxide that causes increased mismatch between the model and reconstruction in other regions.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 9
    Publication Date: 2021-01-04
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 10
    Publication Date: 2021-07-05
    Description: Earth system and climate modelling involves the simulation of processes on a wide range of scales and within and across various compartments of the Earth system. In practice, component models are often developed independently by different research groups, adapted by others to their special interests and then combined using a dedicated coupling software. This procedure not only leads to a strongly growing number of available versions of model components and coupled setups but also to model- and high-performance computing (HPC)-system-dependent ways of obtaining, configuring, building and operating them. Therefore, implementing these Earth system models (ESMs) can be challenging and extremely time consuming, especially for less experienced modellers or scientists aiming to use different ESMs as in the case of intercomparison projects. To assist researchers and modellers by reducing avoidable complexity, we developed the ESM-Tools software, which provides a standard way for downloading, configuring, compiling, running and monitoring different models on a variety of HPC systems. It should be noted that ESM-Tools is not a coupling software itself but a workflow and infrastructure management tool to provide access to increase usability of already existing components and coupled setups. As coupled ESMs are technically the more challenging tasks, we will focus on coupled setups, always implying that stand-alone models can benefit in the same way. With ESM-Tools, the user is only required to provide a short script consisting of only the experiment-specific definitions, while the software executes all the phases of a simulation in the correct order. The software, which is well documented and easy to install and use, currently supports four ocean models, three atmosphere models, two biogeochemistry models, an ice sheet model, an isostatic adjustment model, a hydrology model and a land-surface model. Compared to previous versions, ESM-Tools has lately been entirely recoded in a high-level programming language (Python) and provides researchers with an even more user-friendly interface for Earth system modelling. ESM-Tools was developed within the framework of the Advanced Earth System Model Capacity project, supported by the Helmholtz Association.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 11
    facet.materialart.
    Unknown
    Copernicus
    In:  EPIC3Climate of the Past, Copernicus, 16(4), pp. 1643-1665, ISSN: 1814-9332
    Publication Date: 2021-02-16
    Description: We compare results obtained from modeling the mid-Pliocene warm period using the Community Earth System Models (COSMOS, version: COSMOS-landveg r2413, 2009) with the two different modeling methodologies and sets of boundary conditions prescribed for the two phases of the Pliocene Model Intercomparison Project (PlioMIP), tagged PlioMIP1 and PlioMIP2. Here, we bridge the gap between our contributions to PlioMIP1 (Stepanek and Lohmann, 2012) and PlioMIP2 (Stepanek et al., 2020). We highlight some of the effects that differences in the chosen mid-Pliocene model setup (PlioMIP2 vs. PlioMIP1) have on the climate state as derived with COSMOS, as this information will be valuable in the framework of the model–model and model–data comparison within PlioMIP2. We evaluate the model sensitivity to improved mid-Pliocene boundary conditions using PlioMIP's core mid-Pliocene experiments for PlioMIP1 and PlioMIP2 and present further simulations in which we test model sensitivity to variations in paleogeography, orbit, and the concentration of CO2. Firstly, we highlight major changes in boundary conditions from PlioMIP1 to PlioMIP2 and also the challenges recorded from the initial effort. The results derived from our simulations show that COSMOS simulates a mid-Pliocene climate state that is 0.29°C colder in PlioMIP2 if compared to PlioMIP1 (17.82°C in PlioMIP1, 17.53°C in PlioMIP2; values based on simulated surface skin temperature). On the one hand, high-latitude warming, which is supported by proxy evidence of the mid-Pliocene, is underestimated in simulations of both PlioMIP1 and PlioMIP2. On the other hand, spatial variations in surface air temperature (SAT), sea surface temperature (SST), and the distribution of sea ice suggest improvement of simulated SAT and SST in PlioMIP2 if employing the updated paleogeography. Our PlioMIP2 mid-Pliocene simulation produces warmer SSTs in the Arctic and North Atlantic Ocean than those derived from the respective PlioMIP1 climate state. The difference in prescribed CO2 accounts for 0.5°C of temperature difference in the Arctic, leading to an ice-free summer in the PlioMIP1 simulation, and a quasi ice-free summer in PlioMIP2. Beyond the official set of PlioMIP2 simulations, we present further simulations and analyses that sample the phase space of potential alternative orbital forcings that have acted during the Pliocene and may have impacted geological records. Employing orbital forcing, which differs from that proposed for PlioMIP2 (i.e., corresponding to pre-industrial conditions) but falls into the mid-Pliocene time period targeted in PlioMIP, leads to pronounced annual and seasonal temperature variations. Our result identifies the changes in mid-Pliocene paleogeography from PRISM3 to PRISM4 as the major driver of the mid-Pliocene warmth within PlioMIP and not the minor differences in forcings.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 12
    Publication Date: 2021-07-01
    Description: Palaeoclimate simulations improve our understanding of the climate, inform us about the performance of climate models in a different climate scenario, and help to identify robust features of the climate system. Here, we analyse Arctic warming in an ensemble of 16 simulations of the mid-Pliocene Warm Period (mPWP), derived from the Pliocene Model Intercomparison Project Phase 2 (PlioMIP2). The PlioMIP2 ensemble simulates Arctic (60–90 °N) annual mean surface air temperature (SAT) increases of 3.7 to 11.6 °C compared to the pre-industrial period, with a multi-model mean (MMM) increase of 7.2 °C. The Arctic warming amplification ratio relative to global SAT anomalies in the ensemble ranges from 1.8 to 3.1 (MMM is 2.3). Sea ice extent anomalies range from −3.0 to −10.4×106 km2, with a MMM anomaly of −5.6×106 km2, which constitutes a decrease of 53 % compared to the pre-industrial period. The majority (11 out of 16) of models simulate summer sea-ice-free conditions (≤1×106 km2) in their mPWP simulation. The ensemble tends to underestimate SAT in the Arctic when compared to available reconstructions, although the degree of underestimation varies strongly between the simulations. The simulations with the highest Arctic SAT anomalies tend to match the proxy dataset in its current form better. The ensemble shows some agreement with reconstructions of sea ice, particularly with regard to seasonal sea ice. Large uncertainties limit the confidence that can be placed in the findings and the compatibility of the different proxy datasets. We show that while reducing uncertainties in the reconstructions could decrease the SAT data–model discord substantially, further improvements are likely to be found in enhanced boundary conditions or model physics. Lastly, we compare the Arctic warming in the mPWP to projections of future Arctic warming and find that the PlioMIP2 ensemble simulates greater Arctic amplification than CMIP5 future climate simulations and an increase instead of a decrease in Atlantic Meridional Overturning Circulation (AMOC) strength compared to pre-industrial period. The results highlight the importance of slow feedbacks in equilibrium climate simulations, and that caution must be taken when using simulations of the mPWP as an analogue for future climate change.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 13
    facet.materialart.
    Unknown
    Copernicus
    In:  EPIC3The Cryosphere, Copernicus, 14(11), pp. 3843-3873, ISSN: 1994-0424
    Publication Date: 2020-11-11
    Description: Antarctic geothermal heat flow (GHF) affects the temperature of the ice sheet, determining its ability to slide and internally deform, as well as the behaviour of the continental crust. However, GHF remains poorly constrained, with few and sparse local, borehole-derived estimates and large discrepancies in the magnitude and distribution of existing continent-scale estimates from geophysical models. We review the methods to estimate GHF, discussing the strengths and limitations of each approach; compile borehole and probe-derived estimates from measured temperature profiles; and recommend the following future directions. (1) Obtain more borehole-derived estimates from the subglacial bedrock and englacial temperature profiles. (2) Estimate GHF from inverse glaciological modelling, constrained by evidence for basal melting and englacial temperatures (e.g. using microwave emissivity). (3) Revise geophysically derived GHF estimates using a combination of Curie depth, seismic, and thermal isostasy models. (4) Integrate in these geophysical approaches a more accurate model of the structure and distribution of heat production elements within the crust and considering heterogeneities in the underlying mantle. (5) Continue international interdisciplinary communication and data access.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 14
    Publication Date: 2020-12-07
    Description: Northwestern Alaska has been highly affected by changing climatic patterns with new temperature and precipitation maxima over the recent years. In particular, the Baldwin and northern Seward peninsulas are characterized by an abundance of thermokarst lakes that are highly dynamic and prone to lake drainage like many other regions at the southern margins of continuous permafrost. We used Sentinel-1 synthetic aperture radar (SAR) and Planet CubeSat optical remote sensing data to analyze recently observed widespread lake drainage. We then used synoptic weather data, climate model outputs and lake ice growth simulations to analyze potential drivers and future pathways of lake drainage in this region. Following the warmest and wettest winter on record in 2017/2018, 192 lakes were identified as having completely or partially drained by early summer 2018, which exceeded the average drainage rate by a factor of ∼ 10 and doubled the rates of the previous extreme lake drainage years of 2005 and 2006. The combination of abundant rain- and snowfall and extremely warm mean annual air temperatures (MAATs), close to 0 ∘C, may have led to the destabilization of permafrost around the lake margins. Rapid snow melt and high amounts of excess meltwater further promoted rapid lateral breaching at lake shores and consequently sudden drainage of some of the largest lakes of the study region that have likely persisted for millennia. We hypothesize that permafrost destabilization and lake drainage will accelerate and become the dominant drivers of landscape change in this region. Recent MAATs are already within the range of the predictions by the University of Alaska Fairbanks' Scenarios Network for Alaska and Arctic Planning (UAF SNAP) ensemble climate predictions in scenario RCP6.0 for 2100. With MAAT in 2019 just below 0 ∘C at the nearby Kotzebue, Alaska, climate station, permafrost aggradation in drained lake basins will become less likely after drainage, strongly decreasing the potential for freeze-locking carbon sequestered in lake sediments, signifying a prominent regime shift in ice-rich permafrost lowland regions.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 15
    Publication Date: 2020-07-08
    Description: The ESA Earth Explorer CryoSat-2 was launched on 8 April 2010 to monitor the precise changes in the thickness of terrestrial ice sheets and marine floating ice. To do that, CryoSat orbits the planet at an altitude of around 720 km with a retrograde orbit inclination of 92∘ and a quasi repeat cycle of 369 d (30 d subcycle). To reach the mission goals, the CryoSat products have to meet the highest quality standards to date, achieved through continual improvements of the operational processing chains. The new CryoSat Ice Baseline-D, in operation since 27 May 2019, represents a major processor upgrade with respect to the previous Ice Baseline-C. Over land ice the new Baseline-D provides better results with respect to the previous baseline when comparing the data to a reference elevation model over the Austfonna ice cap region, improving the ascending and descending crossover statistics from 1.9 to 0.1 m. The improved processing of the star tracker measurements implemented in Baseline-D has led to a reduction in the standard deviation of the point-to-point comparison with the previous star tracker processing method implemented in Baseline-C from 3.8 to 3.7 m. Over sea ice, Baseline-D improves the quality of the retrieved heights inside and at the boundaries of the synthetic aperture radar interferometric (SARIn or SIN) acquisition mask, removing the negative freeboard pattern which is beneficial not only for freeboard retrieval but also for any application that exploits the phase information from SARIn Level 1B (L1B) products. In addition, scatter comparisons with the Beaufort Gyre Exploration Project (BGEP; https://www.whoi.edu/beaufortgyre, last access: October 2019) and Operation IceBridge (OIB; Kurtz et al., 2013) in situ measurements confirm the improvements in the Baseline-D freeboard product quality. Relative to OIB, the Baseline-D freeboard mean bias is reduced by about 8 cm, which roughly corresponds to a 60 % decrease with respect to Baseline-C. The BGEP data indicate a similar tendency with a mean draft bias lowered from 0.85 to −0.14 m. For the two in situ datasets, the root mean square deviation (RMSD) is also well reduced from 14 to 11 cm for OIB and by a factor of 2 for the BGEP. Observations over inland waters show a slight increase in the percentage of good observations in Baseline-D, generally around 5 %–10 % for most lakes. This paper provides an overview of the new Level 1 and Level 2 (L2) CryoSat Ice Baseline-D evolutions and related data quality assessment, based on results obtained from analyzing the 6-month Baseline-D test dataset released to CryoSat expert users prior to the final transfer to operations.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 16
    Publication Date: 2020-08-10
    Description: The Global Ocean Data Analysis Project (GLODAP) is a synthesis effort providing regular compilations of surface to bottom ocean biogeochemical data, with an emphasis on seawater inorganic carbon chemistry and related variables determined through chemical analysis of water samples. GLODAPv2.2020 is an update of the previous version, GLODAPv2.2019. The major changes are: data from 106 more cruises added, extension of time coverage until 2019, and the inclusion of available discrete fugacity of CO2 (fCO2) values in the merged product files. GLODAPv2.2020 includes measurements from more than 1.2 million water samples from the global oceans collected on 946 cruises. The data for the 12 GLODAP core variables (salinity, oxygen, nitrate, silicate, phosphate, dissolved inorganic carbon, total alkalinity, pH, CFC-11, CFC-12, CFC-113, and CCl4) have undergone extensive quality control, especially systematic evaluation of bias. The data are available in two formats: (i) as submitted by the data originator but updated to WOCE exchange format and (ii) as a merged data product with adjustments applied to minimize bias. These adjustments were derived by comparing the data from the 106 new cruises with the data from the 840 quality-controlled cruises of the GLODAPv2.2019 data product. They correct for errors related to measurement, calibration, and data handling practices, while taking into account any known or likely time trends or variations in the variables evaluated. The compiled and adjusted data product is believed to be consistent to better than 0.005 in salinity, 1 % in oxygen, 2 % in nitrate, 2 % in silicate, 2 % in phosphate, 4 μmol kg−1 in dissolved inorganic carbon, 4 μmol kg−1 in total alkalinity, 0.01–0.02, depending on region, in pH, and 5 % in the halogenated transient tracers. The other variables included in the compilation, such as isotopic tracers and discrete fCO2 were not subjected to bias comparison or adjustments. The original data, their documentation and doi codes are available at the Ocean Carbon Data System of NOAA NCEI (https://www.nodc.noaa.gov/ocads/oceans/GLODAPv2_2020/, last access: 22 June 2020). This site also provides access to the merged data product, which is provided as a single global file and as four regional ones – the Arctic, Atlantic, Indian, and Pacific oceans – under https://doi.org/10.25921/2c8h-sa89 (Olsen et al., 2020). The bias corrected product files also include significant ancillary and approximated data. These were obtained by interpolation of, or calculation from, measured data. This living data update documents the GLODAPv2.2020 methods and provides a broad overview of the secondary quality control procedures and results.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , notRev
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 17
    facet.materialart.
    Unknown
    Copernicus
    In:  EPIC3Geochemical evidence of a floating Arctic ice sheet and underlying freshwater in the Arctic Mediterranean in glacial periods, EGU General Assembly 2021, Copernicus, pp. EGU21-12910
    Publication Date: 2021-05-01
    Description: Numerous studies have addressed the possible existence of large floating ice sheets in the glacial Arctic Ocean from theoretical, modelling, or seafloor morphology perspectives. Here, we add evidence from the sediment record that support the existence of such freshwater ice caps in certain intervals, and we discuss their implications for possible non-linear and rapid behaviour of such a system in the high latitudes. We present sedimentary activities of 230Th together with 234U/238U ratios, the concentrations of manganese, sulphur and calcium in the context of lithological information and records of microfossils and their isotope composition. New analyses (PS51/038, PS72/396) and a re-analysis of existing marine sediment records (PS1533, PS1235, PS2185, PS2200, amongst others) in view of the naturally occurring radionuclide 230Thex and, where available, 10Be from the Arctic Ocean and the Nordic Seas reveal the widespread occurrence of intervals with a specific geochemical signature. The pattern of these parameters in a pan-Arctic view can best be explained when assuming the repeated presence of freshwater in frozen and liquid form across large parts of the Arctic Ocean and the Nordic Seas. Based on the sedimentary evidence and known environmental constraints at the time, we develop a glacial scenario that explains how these ice sheets, together with eustatic sea-level changes, may have affected the past oceanography of the Arctic Ocean in a fundamental way that must have led to a drastic and non-linear response to external forcing. This concept offers a possibility to explain and to some extent reconcile contrasting age models for the Late Pleistocene in the Arctic Ocean. Our view, if adopted, offers a coherent dating approach across the Arctic Ocean and the Nordic Seas, linked to events outside the Arctic.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , notRev
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 18
    Publication Date: 2020-02-17
    Description: Glacial isostatic adjustment (GIA) is a major source of uncertainty for ice and ocean mass balance estimates derived from satellite gravimetry. In Antarctica the gravimetric effect of cryospheric mass change and GIA are of the same order of magnitude. Inverse estimates from geodetic observations hold some promise for mass signal separation. Here, we investigate the combination of satellite gravimetry and altimetry and demonstrate that the choice of input data sets and processing methods will influence the resultant GIA inverse estimate. This includes the combination that spans the full GRACE record (April 2002–August 2016). Additionally, we show the variations that arise from combining the actual time series of the differing data sets. Using the inferred trends, we assess the spread of GIA solutions owing to (1) the choice of different degree-1 and C20 products, (2) viable candidate surface-elevation-change products derived from different altimetry missions corresponding to different time intervals, and (3) the uncertainties associated with firn process models. Decomposing the total-mass signal into the ice mass and the GIA components is strongly dependent on properly correcting for an apparent bias in regions of small signal. Here our ab initio solutions force the mean GIA and GRACE trend over the low precipitation zone of East Antarctica to be zero. Without applying this bias correction, the overall spread of total-mass change and GIA-related mass change using differing degree-1 and C20 products is 68 and 72 Gt a−1, respectively, for the same time period (March 2003–October 2009). The bias correction method collapses this spread to 6 and 5 Gt a−1, respectively. We characterize the firn process model uncertainty empirically by analysing differences between two alternative surface mass balance products. The differences propagate to a 10 Gt a−1 spread in debiased GIA-related mass change estimates. The choice of the altimetry product poses the largest uncertainty on debiased mass change estimates. The spread of debiased GIA-related mass change amounts to 15 Gt a−1 for the period from March 2003 to October 2009. We found a spread of 49 Gt a−1 comparing results for the periods April 2002–August 2016 and July 2010–August 2016. Our findings point out limitations associated with data quality, data processing, and correction for apparent biases.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 19
    Publication Date: 2021-03-25
    Description: Landfast sea ice (fast ice) attached to Antarctic (near-)coastal elements is a critical component of the local physical and ecological systems. Through its direct coupling with the atmosphere and ocean, fast-ice properties are also a potential indicator of processes related to a changing climate. However, in situ fast-ice observations in Antarctica are extremely sparse because of logistical challenges and harsh environmental conditions. Since 2010, a monitoring program observing the seasonal evolution of fast ice in Atka Bay has been conducted as part of the Antarctic Fast Ice Network (AFIN). The bay is located on the northeastern edge of Ekström Ice Shelf in the eastern Weddell Sea, close to the German wintering station Neumayer III. A number of sampling sites have been regularly revisited each year between annual ice formation and breakup to obtain a continuous record of sea-ice and sub-ice platelet-layer thickness, as well as snow depth and freeboard across the bay. Here, we present the time series of these measurements over the last 9 years. Combining them with observations from the nearby Neumayer III meteorological observatory as well as auxiliary satellite images enables us to relate the seasonal and interannual fast-ice cycle to the factors that influence their evolution. On average, the annual consolidated fast-ice thickness at the end of the growth season is about 2 m, with a loose platelet layer of 4 m thickness beneath and 0.70 m thick snow on top. Results highlight the predominately seasonal character of the fast-ice regime in Atka Bay without a significant interannual trend in any of the observed variables over the 9-year observation period. Also, no changes are evident when comparing with sporadic measurements in the 1980s and 1990s. It is shown that strong easterly winds in the area govern the year-round snow distribution and also trigger the breakup of fast ice in the bay during summer months. Due to the substantial snow accumulation on the fast ice, a characteristic feature is frequent negative freeboard, associated flooding of the snow–ice interface, and a likely subsequent snow ice formation. The buoyant platelet layer beneath negates the snow weight to some extent, but snow thermodynamics is identified as the main driver of the energy and mass budgets for the fast-ice cover in Atka Bay. The new knowledge of the seasonal and interannual variability of fast-ice properties from the present study helps to improve our understanding of interactions between atmosphere, fast ice, ocean, and ice shelves in one of the key regions of Antarctica and calls for intensified multidisciplinary studies in this region.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , peerRev
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 20
    Publication Date: 2021-07-01
    Description: The Pliocene epoch has great potential to improve our understanding of the long-term climatic and environmental consequences of an atmospheric CO2 concentration near ∼400 parts per million by volume. Here we present the large-scale features of Pliocene climate as simulated by a new ensemble of climate models of varying complexity and spatial resolution based on new reconstructions of boundary conditions (the Pliocene Model Intercomparison Project Phase 2; PlioMIP2). As a global annual average, modelled surface air temperatures increase by between 1.7 and 5.2 °C relative to the pre-industrial era with a multi-model mean value of 3.2 °C. Annual mean total precipitation rates increase by 7 % (range: 2 %–13 %). On average, surface air temperature (SAT) increases by 4.3 °C over land and 2.8 °C over the oceans. There is a clear pattern of polar amplification with warming polewards of 60°N and 60°S exceeding the global mean warming by a factor of 2.3. In the Atlantic and Pacific oceans, meridional temperature gradients are reduced, while tropical zonal gradients remain largely unchanged. There is a statistically significant relationship between a model's climate response associated with a doubling in CO2 (equilibrium climate sensitivity; ECS) and its simulated Pliocene surface temperature response. The mean ensemble Earth system response to a doubling of CO2 (including ice sheet feedbacks) is 67 % greater than ECS; this is larger than the increase of 47 % obtained from the PlioMIP1 ensemble. Proxy-derived estimates of Pliocene sea surface temperatures are used to assess model estimates of ECS and give an ECS range of 2.6–4.8°C. This result is in general accord with the ECS range presented by previous Intergovernmental Panel on Climate Change (IPCC) Assessment Reports.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 21
    Publication Date: 2021-06-16
    Description: In the last decades, changing climate conditions have had a severe impact on sea ice at the western Antarctic Peninsula (WAP), an area rapidly transforming under global warming. To study the development of spring sea ice and environmental conditions in the pre-satellite era we investigated three short marine sediment cores for their biomarker inventory with a particular focus on the sea ice proxy IPSO25 and micropaleontological proxies. The core sites are located in the Bransfield Strait in shelf to deep basin areas characterized by a complex oceanographic frontal system, coastal influence and sensitivity to large-scale atmospheric circulation patterns. We analyzed geochemical bulk parameters, biomarkers (highly branched isoprenoids, glycerol dialkyl glycerol tetraethers, sterols), and diatom abundances and diversity over the past 240 years and compared them to observational data, sedimentary and ice core climate archives, and results from numerical models. Based on biomarker results we identified four different environmental units characterized by (A) low sea ice cover and high ocean temperatures, (B) moderate sea ice cover with decreasing ocean temperatures, (C) high but variable sea ice cover during intervals of lower ocean temperatures, and (D) extended sea ice cover coincident with a rapid ocean warming. While IPSO25 concentrations correspond quite well to satellite sea ice observations for the past 40 years, we note discrepancies between the biomarker-based sea ice estimates, the long-term model output for the past 240 years, ice core records, and reconstructed atmospheric circulation patterns such as the El Niño–Southern Oscillation (ENSO) and Southern Annular Mode (SAM). We propose that the sea ice biomarker proxies IPSO25 and PIPSO25 are not linearly related to sea ice cover, and, additionally, each core site reflects specific local environmental conditions. High IPSO25 and PIPSO25 values may not be directly interpreted as referring to high spring sea ice cover because variable sea ice conditions and enhanced nutrient supply may affect the production of both the sea-ice-associated and phytoplankton-derived (open marine, pelagic) biomarker lipids. For future interpretations we recommend carefully considering individual biomarker records to distinguish between cold sea-ice-favoring and warm sea-ice-diminishing environmental conditions.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 22
    Publication Date: 2021-07-01
    Description: The modeling of paleoclimate, using physically based tools, is increasingly seen as a strong out-of-sample test of the models that are used for the projection of future climate changes. New to the Coupled Model Intercomparison Project (CMIP6) is the Tier 1 Last Interglacial experiment for 127 000 years ago (lig127k), designed to address the climate responses to stronger orbital forcing than the midHolocene experiment, using the same state-of-the-art models as for the future and following a common experimental protocol. Here we present a first analysis of a multi-model ensemble of 17 climate models, all of which have completed the CMIP6 DECK (Diagnostic, Evaluation and Characterization of Klima) experiments. The equilibrium climate sensitivity (ECS) of these models varies from 1.8 to 5.6 ∘C. The seasonal character of the insolation anomalies results in strong summer warming over the Northern Hemisphere continents in the lig127k ensemble as compared to the CMIP6 piControl and much-reduced minimum sea ice in the Arctic. The multi-model results indicate enhanced summer monsoonal precipitation in the Northern Hemisphere and reductions in the Southern Hemisphere. These responses are greater in the lig127k than the CMIP6 midHolocene simulations as expected from the larger insolation anomalies at 127 than 6 ka. New synthesis for surface temperature and precipitation, targeted for 127 ka, have been developed for comparison to the multi-model ensemble. The lig127k model ensemble and data reconstructions are in good agreement for summer temperature anomalies over Canada, Scandinavia, and the North Atlantic and for precipitation over the Northern Hemisphere continents. The model–data comparisons and mismatches point to further study of the sensitivity of the simulations to uncertainties in the boundary conditions and of the uncertainties and sparse coverage in current proxy reconstructions. The CMIP6–Paleoclimate Modeling Intercomparison Project (PMIP4) lig127k simulations, in combination with the proxy record, improve our confidence in future projections of monsoons, surface temperature, and Arctic sea ice, thus providing a key target for model evaluation and optimization.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 23
    facet.materialart.
    Unknown
    Copernicus
    In:  EPIC3A global monthly climatology of oceanic total dissolved inorganic carbon: a neural network approach, Earth System Science Data Discussions, Copernicus, pp. 1-30
    Publication Date: 2020-03-17
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , notRev
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 24
    Publication Date: 2021-09-20
    Description: In order to investigate the impact of spatial resolution on the discrepancy between simulated δ18O and observed δ18O in Greenland ice cores, regional climate simulations are performed with the isotope-enabled regional climate model (RCM) COSMO_iso. For this purpose, isotope-enabled general circulation model (GCM) simulations with the ECHAM5-wiso general circulation model (GCM) under present-day conditions and the MPI-ESM-wiso GCM under mid-Holocene conditions are dynamically downscaled with COSMO_iso for the Arctic region. The capability of COSMO_iso to reproduce observed isotopic ratios in Greenland ice cores for these two periods is investigated by comparing the simulation results to measured δ18O ratios from snow pit samples, Global Network of Isotopes in Precipitation (GNIP) stations and ice cores. To our knowledge, this is the first time that a mid-Holocene isotope-enabled RCM simulation is performed for the Arctic region. Under present-day conditions, a dynamical downscaling of ECHAM5-wiso (1.1◦ × 1.1◦) with COSMO_iso to a spatial resolution of 50km improves the agreement with the measured δ18O ratios for 14 of 19 observational data sets. A further increase in the spatial resolution to 7km does not yield substantial improvements except for the coastal areas with its complex terrain. For the mid-Holocene, a fully coupled MPI-ESM-wiso time slice simulation is downscaled with COSMO_iso to a spatial resolution of 50km. In the mid-Holocene, MPI-ESM-wiso already agrees well with observations in Greenland and a downscaling with COSMO_iso does not further improve the model–data agreement. Despite this lack of improvement in model biases, the study shows that in both periods, observed δ18O values at measurement sites constitute isotope ratios which are mainly within the subgrid-scale variability of the global ECHAM5-wiso and MPI-ESM-wiso simulation results. The correct δ18O ratios are consequently not resolved in the GCM simulation results and need to be extracted by a refinement with an RCM. In this context, the RCM simulations provide a spatial δ18O distribution by which the effects of local uncertainties can be taken into account in the comparison between point measurements and model outputs. Thus, an isotope-enabled GCM–RCM model chain with realistically implemented fractionating processes constitutes a useful supplement to reconstruct regional paleo-climate conditions during the mid-Holocene in Greenland. Such model chains might also be applied to reveal the full potential of GCMs in other regions and climate periods, in which large deviations relative to observed isotope ratios are simulated.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 25
    Publication Date: 2021-09-20
    Description: Proxy climate records are an invaluable source of information about the earth’s climate prior to the instrumental record. The temporal- and spatial-coverage of records continues to increase, however, these records of past climate are associated with significant uncertainties due to non-climate processes that influence the recorded and measured proxy values. Generally, these uncertainties are timescale-dependent and correlated in time. Accounting for structure in the errors is essential to providing realistic error estimates for smoothed or stacked records, detection of anomalies and identifying trends, but this structure is seldom accounted for. In the first of these companion articles we outlined a theoretical framework for handling proxy uncertainties by deriving the power spectrum of proxy error components from which it is possible to obtain timescale-dependent error estimates. Here in part II, we demonstrate the practical application of this theoretical framework using the example of marine sediment cores. We consider how to obtain estimates for the required parameters and give examples of the application of this approach for typical marine sediment proxy records. Our new approach of estimating and providing timescale-dependent proxy errors overcomes the limitations of simplistic single value error estimates. We aim to provide the conceptual basis for a more quantitative use of paleo-records for applications such as model-data comparison, regional and global synthesis of past climate states and data assimilation.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev , info:eu-repo/semantics/article
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 26
    Publication Date: 2021-09-06
    Description: The mid-Pliocene warm period (mPWP; ∼3.2 million years ago) is seen as the most recent time period characterized by a warm climate state, with similar to modern geography and ∼400 ppmv atmospheric CO2 concentration, and is therefore often considered an interesting analogue for near-future climate projections. Paleoenvironmental reconstructions indicate higher surface temperatures, decreasing tropical deserts, and a more humid climate in West Africa characterized by a strengthened West African Monsoon (WAM). Using model results from the second phase of the Pliocene Modelling Intercomparison Project (PlioMIP2) ensemble, we analyse changes of the WAM rainfall during the mPWP by comparing them with the control simulations for the pre-industrial period. The ensemble shows a robust increase in the summer rainfall over West Africa and the Sahara region, with an average increase of 2.5 mm/d, contrasted by a rainfall decrease over the equatorial Atlantic. An anomalous warming of the Sahara and deepening of the Saharan Heat Low, seen in 〉90 % of the models, leads to a strengthening of the WAM and an increased monsoonal flow into the continent. A similar warming of the Sahara is seen in future projections using both phase 3 and 5 of the Coupled Model Intercomparison Project (CMIP3 and CMIP5). Though previous studies of future projections indicate a west–east drying–wetting contrast over the Sahel, PlioMIP2 simulations indicate a uniform rainfall increase in that region in warm climates characterized by increasing greenhouse gas forcing. We note that this effect will further depend on the long-term response of the vegetation to the CO2 forcing.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 27
    Publication Date: 2021-12-15
    Description: Due to its dryness, the subtropical free troposphere plays a critical role in the radiative balance of the Earth's climate system. But the complex interactions of the dynamical and physical processes controlling the variability in the moisture budget of this sensitive region of the subtropical atmosphere are still not fully understood. Stable water isotopes can provide important information about several of the latter processes, namely subsidence drying, turbulent mixing, and dry and moist convective moistening. In this study, we use high-resolution simulations of the isotope-enabled version of the regional weather and climate prediction model of the Consortium for Small-Scale Modelling (COSMOiso) to investigate predominant moisture transport pathways in the Canary Islands region in the eastern subtropical North Atlantic. Comparison of the simulated isotope signals with multi-platform isotope observations (aircraft, ground- and space-based remote sensing) from a field campaign in summer 2013 shows that COSMOiso can reproduce the observed variability of stable water vapour isotopes on timescales of hours to days, thus allowing us to study the mechanisms that control the subtropical free-tropospheric humidity. Changes in isotopic signals along backward trajectories from the Canary Islands region reveal the physical processes behind the synoptic-scale isotope variability. We identify four predominant moisture transport pathways of mid-tropospheric air, each with distinct isotopic signatures: - air parcels originating from the convective boundary layer of the Saharan heat low (SHL) – these are characterised by a homogeneous isotopic composition with a particularly high δD (median mid-tropospheric δD=−122‰), which results from dry convective mixing of low-level moisture of diverse origin advected into the SHL; - air parcels originating from the free troposphere above the SHL – although experiencing the largest changes in humidity and δD during their subsidence over West Africa, these air parcels typically have lower δD values (median δD=−148‰) than air parcels originating from the boundary layer of the SHL; - air parcels originating from outside the SHL region, typically descending from tropical upper levels south of the SHL, which are often affected by moist convective injections from mesoscale convective systems in the Sahel – their isotopic composition is much less enriched in heavy isotopes (median δD=−175‰) than those from the SHL region; - air parcels subsiding from the upper-level extratropical North Atlantic – this pathway leads to the driest and most depleted conditions (median δD=−255‰) in the middle troposphere near the Canary Islands. The alternation of these transport pathways explains the observed high variability in humidity and δD on synoptic timescales to a large degree. We further show that the four different transport pathways are related to specific large-scale flow conditions. In particular, distinct differences in the location of the North African mid-level anticyclone and of extratropical Rossby wave patterns occur between the four transport pathways. Overall, this study demonstrates that the adopted Lagrangian isotope perspective enhances our understanding of air mass transport and mixing and offers a sound interpretation of the free-tropospheric variability of specific humidity and isotope composition on timescales of hours to days in contrasting atmospheric conditions over the eastern subtropical North Atlantic.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 28
    Publication Date: 2021-12-21
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev , info:eu-repo/semantics/article
    Format: application/pdf
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 29
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3820-3831 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: In this paper we apply the recently developed state-specific multireference coupled-cluster and perturbation theories to calculate electrical properties such as dipole moment and static polarizability using perturbed orbitals in finite fields. The theories are built on complete active space reference functions, and are designed to treat quasidegeneracy of varying degrees while bypassing the intruder problem. Numerical results are presented for the model systems H4 with trapezoidal geometry and the lowest two singlet states of CH2. Both the systems require a multireference formulation due to quasidegeneracy. In the field-free situation, the former encounters intruders at an intermediate trapezoidal geometry in the traditional treatment using effective Hamiltonians, while the latter shows a pronounced multireference character in the two singlet states. This affects the response properties in the presence of a perturbing field. A comparison with the full CI results in the same basis indicates the efficacy of the state-specific methods in wide ranges of geometries, even when the traditional effective Hamiltonian based methods fail due to intruders. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 30
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3812-3819 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A compact basis set is constructed for the water dimer by focusing directly on an optimal description of the counterpoise-corrected interaction energy (ΔE) rather than on the total energy of the fragments. The optimization criterion is that the basis set should be of uniform accuracy, i.e., the truncation error in ΔE due to the basis set incompleteness should be the same for all symmetry types at all sites. Aiming at a truncation error of 10 μhartree per symmetry at the SCF+MP2 (self-consistent field+Møller–Plesset second-order) frozen core level the resulting interaction optimized basis set comprises 249 functions. The composition of this IO249 set is O/5s3p4d3f2g1h, H(donor)/2s4p1d, H(else)/2s3p, bond function set/3s3p2d1f. An all-electron variant, IO275, is described as well. A recipe to obtain interaction optimized sets for other systems is given. The set IO249 yields a ΔE(fc) value at the Feller–Frisch geometry of −4.87 kcal/mol. Of the many orbital-based calculations that have been reported for this system only Schütz' 1046-function calculation [J. Chem. Phys. 107, 4597 (1997)] was more accurate. The small size of the interaction optimized sets opens the possibility for high-accuracy SCF+MP2 work on larger systems than have been accessible before. It also brings higher-level correlated treatments within reach. An Appendix summarizes two additivity rules which allow the ΔE for a larger basis set to be estimated to very high accuracy from the results of smaller basis sets. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 31
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3832-3836 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: In this paper we present Z-vector formalism for the Fock space multireference coupled cluster framework. We present detailed equations describing the derivative effective Hamiltonian, where the response amplitudes of the highest Fock sector are eliminated. We discuss the conditions and approximations under which the formalism is possible. We also discuss the implications and comparison with the similar formalism in the single reference framework. The computational advantages and feasibility are also commented upon in this paper. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 32
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3837-3845 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Ten low-lying electronic states of Fe(II) porphine, 5A1g, 5Eg, 5B2g, 3A2g, 3B2g, 3Eg(A), 3Eg(B), 1A1g, 1B2g, and 1Eg states, are studied with multiconfigurational second-order perturbation (CASPT2) calculations with complete active space self-consistent field (CASSCF) reference functions with larger active space and basis sets. The enlargement of active space and basis sets has no influence on the conclusion of a previous multireference Møller–Plesset perturbation (MRMP) study. The present CASPT2 calculation concludes that the 5A1g state is the ground state. A relativistic correction has been performed by the relativistic scheme of eliminating small components (RESC). For energetics, no significant contribution from the relativistic correction was found. The relative energies and orbital energies are not changed appreciably by the introduction of a relativistic correction. The present result does not agree with all the spectroscopic observations, but is consistent with a magnetic moment study. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 33
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3846-3854 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The two-body interaction energies of the cyclic (C3h) and noncyclic (C2) trimers at the basis set limit (15.55 and 16.55 kJ/mol) were estimated by means of second-order Møller–Plesset perturbation theory including terms linear in the interelectronic distance (MP2-R12 approach). Coupled cluster calculations with single and double substitutions and with noniterative triple excitations [CCSD(T)] were carried out to correct the MP2-R12 two-body interaction energies for the effect of higher excitations, and also for the evaluation of the three-body interaction energies. The calculated bonding energies of the trimers using this model calculation (16.82 and 17.20 kJ/mol) suggest that the two isomers are nearly isoenergetic. The three-body terms are small (only of the order of 1 kJ/mol), stabilizing the cyclic trimer, but destabilizing the noncyclic trimer. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 34
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3855-3861 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The structure and the relative stability of the ethanol dimer and the cyclic ethanol trimer were studied using density functional theory methods. The geometries of the different dimers and trimers were optimized at the B3LYP/6-311+G(d,p) level of theory, while the final energies were obtained at the B3LYP/6-311+G(3df,2p) level. Four different (ethanol)2 complexes were found to be local minima of the potential energy surface, the global minimum being that in which both monomers exhibit a trans conformation. The hydrogen bond (HB) in ethanol dimer is slightly stronger than in methanol dimer, reflecting the enhanced intrinsic basicity of ethanol with regards to methanol. The OH donor stretch appears redshifted by 161 cm−1, while the redshifting undergone by the OH acceptor stretch is negligibly small. The relative stability of the trimers is a function of the number of monomers with a gauche conformation, the global minimum being that in which the three monomers have a trans conformation. As for water and methanol trimers, the three HBs in the cyclic ethanol trimer are not strictly equivalent. Consistently, the redshiftings of the OH stretching frequencies are different. Cooperative effects are sizably large, as reflected in the O(centered ellipsis)O distances, the elongation of the OH donor groups, the charge density at the bond critical points, the frequency shiftings of the OH stretches, and the additivity interaction energy. The most significant features of the vibrational spectra of the monomers, the dimers, and the trimers in the 800–1200 cm−1 region are reasonably well reproduced by our calculations.© 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 35
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3862-3873 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A new potential energy surface for the lowest 3A″ electronic state of the O(3P)+HCl system is presented. This surface is based on electronic energies calculated at the multireference configuration interaction level of theory with the Davidson correction (MR-CI+Q) using the Dunning cc-pVTZ one-electron basis sets. The ab initio energies thus obtained are scaled using the scaled external correlation (SEC) method of Brown and Truhlar. The SEC-scaled energies are fitted to a simple analytical expression to yield a potential energy surface which correlates the reactants O(3P)+HCl(1Σ+) to the products OH(2Π)+Cl(2P). The reaction barrier on this surface lies at an O–H–Cl angle of 131.4° at an energy of 9.78 kcal/mol above the asymptotic O+HCl minimum. This barrier is 1.3 kcal/mol higher than that on the potential energy surface obtained by Koizumi, Schatz, and Gordon (KSG) [J. Chem. Phys. 95, 6421 (1991)] and 1.1 kcal/mol lower than the S2 surface of Ramachandran, Senekowitsch, and Wyatt (RSW) [J. Mol. Struct. (Theochem) 454, 307 (1998)]. The dynamics of the reaction O(3P)+HCl(v=2; j=1,6,9)→OH(v′,j′)+Cl on this potential surface is studied using quasi-classical trajectory (QCT) propagation and the results are compared to the experimental observations of Zhang et al. [R. Zhang, W. J. van der Zande, M. J. Bronikowski, and R. N. Zare, J. Chem. Phys. 94, 2704 (1991)]. The broad distribution of collision energies in the experiment is modeled by computing weighted averages of the quantities of interest with the weighting factor at each collision energy determined by the collision energy distribution. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 36
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 2103-2108 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The vapor–liquid coexistence densities for water near the critical point were determined using a polarizable ab initio based model and grand canonical Monte Carlo simulations combined with the histogram reweighting technique. The predictions of the model used, which is found to give good agreement with experimental data at ambient conditions, are far below the experimental critical temperature and density. The saturation pressure is also overestimated. The source of this discrepancy may be related to the high pressure that the model exhibits even for liquid water. Since there is no fitting to experimental data, it is possible to refine the potential in a systematic way. In particular, an improvement in the sampling of the ab initio calculation for the repulsive part of the intermolecular potential is suggested in order to obtain better agreement with experiment at high temperatures and pressures. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 37
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 2143-2150 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A model to investigate a gel-to-zeolite transformation as a possible growth mechanism through association and rearrangements of extended precursor structures is developed and solved via continuum time lattice Monte Carlo simulations. The model is used to study the morphology of zeolite L nanocrystals grown from an initial amorphous microporous precursor gel. The model considers gel dissolution to release growth precursor extended structures, precursor migration, precursor–precursor association, precursor incorporation into zeolite nanoparticles, and zeolite dissolution. It is shown that the gel-to-zeolite transformation can occur when dissolved precursor migration is slow compared to precursor incorporation and zeolite dissolution. Under these conditions, the initial gel microstructure (intraparticle porosity) has a significant effect on the zeolite morphology and on the crystallization kinetics. This transformation proceeds in two stages: A zeolitic framework forms initially without long-range order, followed by slow rearrangement of building units into nanocrystalline particles with possible defects. Finally different growth modes are identified as a function of microkinetic parameters and gel morphology. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 38
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 2157-2163 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The electronic structure of tris(8-hydroxyquinoline) aluminum (Alq3) has been studied in the pristine molecular solid state as well as upon interaction (doping) with potassium and lithium. We discuss the results of a joint theoretical and experimental investigation, based on a combination of x-ray and ultraviolet photoelectron spectroscopies with quantum-chemical calculations at the density functional theory level. Upon doping, each electron transferred from an alkali metal atom is stored on one of the three ligands of the Alq3 molecule, resulting in a new spectral feature (peak) in the valence band that evolves uniformly when going from a doping level of one to three metal atoms per Alq3 molecule. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 39
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 2151-2156 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A fluid with an interaction potential consisting of a hard core and an attractive Yukawa tail is considered. The strength of the attraction is taken to depend both on density and temperature in order to take into account the state dependence of the effective interaction suggested by the analysis of structural data of several colloidal suspensions, in particular microemulsions of AOT reverse micelles. The thermodynamics of this fluid is investigated starting from the inverse temperature expansion of the free energy in the mean spherical approximation. The temperature and density dependence of the interaction is incorporated in consistent expressions for the pressure, isothermal compressibility, and chemical potential. The phase diagram predicted by this method is in agreement with experimental data on AOT reverse micelles analyzed in the effective one component approach. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 40
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 2176-2180 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The size-dependent melting temperature and the size-dependent melting entropy of organic nanocrystals are predicted by use of our simple model being free of any adjustable parameter. The model predictions for the size-dependent melting temperature and the size-dependent melting entropy are supported by the experimental results on benzene, chlorobenzene, heptane, and naphthalene nanocrystals. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 41
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 2169-2175 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The O2 adsorption on Ag(111) single crystal in the range of 300–500 K has been studied by XPS, ADXPS, and TPD. At room temperature, the O1s line observed at 530.0 eV goes down to 528.2 eV when the sample is heated to 420 K. The comparison of XPS and TPD data indicates that both lines can be assigned to chemisorbed atomic oxygen. The depth concentration profiles calculated on the basis of the angular-dependent XPS data show that the line at 530.0 eV is responsible for oxygen adsorbed at the surface, as opposed to that at 528.2 eV which is assigned to oxygen between the top and second silver layers. The formation of surface silver oxide is concluded in the latter case. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 42
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 2181-2189 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We report the results of self-consistent quantum Monte Carlo simulations of the structure of the liquid-vapor interface of the alloy Sn0.09Ga0.81. Our calculations are in very good agreement with the experimental results reported by Lei, Huang and Rice [J. Chem. Phys. 107, 4051 (1997)]. In particular, our calculations confirm the experimentally inferred existence of a partial second layer of Sn below the complete outermost layer of Sn in the stratified liquid-vapor interface of this alloy. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 43
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3929-3939 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: In this paper, we present detailed quantum treatment of the semirigid vibrating rotor target (SVRT) model for reaction dynamics involving polyatomic molecules. In the SVRT model, the reacting (target) molecule is treated as a semirigid vibrating rotor which can be considered as a three-dimensional generalization of the diatomic molecule. This model provides a realistic framework to treat reaction dynamics of polyatomic systems. Using the SVRT model, it becomes computationally practical to carry out quantitatively accurate quantum dynamics calculation for a variety of dynamics problems in which the reacting molecule is a polyatomic or complex molecule. In this work, specific theoretical treatment and mathematical formulation of the SVRT model are presented for three general classes of reaction systems: (1) reaction of an atom with a polyatomic molecule (atom–polyatom reaction), (2) reaction between two polyatomic molecules (polyatom–polyatom reaction), and (3) polyatomic reaction with a rigid surface (polyatom–surface reaction). Since the number of dynamical degrees of freedom in the SVRT model for the above three classes of dynamical problems is limited, accurate quantum (both ab initio and dynamical) calculations are possible for many reactions of practical chemical interest. In this paper, a time-dependent wave packet approach is employed to implement the SVRT model for dynamics calculation of polyatomic reactions. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 44
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3919-3928 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A pulsed molecular beam cavity Fourier transform microwave spectrometer was used to measure pure rotational spectra of nine isotopomers of Ne2–N2O, and of three isotopomers of the Ar2–N2O van der Waals trimer. For Ne2–N2O, these are 20Ne20Ne–14N14N16O, 20Ne22Ne–14N14N16O, 22Ne22Ne–14N14N16O, 20Ne20Ne–15N14N16O, 20Ne22Ne–15N14N16O, 22Ne22Ne–15N14N16O, 20Ne20Ne–14N15N16O, 20Ne22Ne–14N15N16O, and 22Ne22Ne–14N15N16O. Those for Ar2–N2O are 40Ar40Ar–14N14N16O, 40Ar40Ar–15N14N16O, and 40Ar40Ar–14N15N16O. The spectra were measured in the frequency range between 3 and 18 GHz. Both a- and c-type transitions were measured for all Ne2–N2O isotopomers. In the case of the mixed, 20Ne22Ne containing, isotopomers a small b-dipole moment occurs and two b-type transitions were measured. In the spectra of Ar2–N2O only b- and c-type transitions were measured. Rotational and centrifugal distortion constants were determined for all the isotopomers of each complex. The spectral analyses show that Ne2–N2O is a highly asymmetric prolate rotor (κ=−0.158 for 20Ne20Ne–14N14N16O) while Ar2–N2O is a highly asymmetric oblate rotor (κ=0.285 for 40Ar40Ar–14N14N16O). Both trimers were found to have distorted tetrahedral structures with the rare gases tilted towards the O atom of the N2O subunit. Nuclear quadrupole hyperfine structures due to both terminal and central 14N nuclei were observed and analyzed to give the nuclear quadrupole coupling constants, χaa(1), χbb(1) and χaa(2), χbb(2). The resulting spectroscopic constants were utilized to derive ground state effective structures, ground state average structures, and partial substitution structures. Harmonic force field analyses were performed for each complex using the obtained quartic centrifugal distortion constants. The results of the spectroscopic analyses are discussed in the light of possible three-body nonadditive interactions. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 45
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3940-3945 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Photodissociation of the H2S molecule at 157.6 nm was studied experimentally using the Rydberg tagging technique. Translational energy distributions of the H-atom product from the H2S photodissociation were measured, and the SH(X 2Π)+H(2S) channel was found to be the dominant dissociation process. Spin-orbit and rovibrational state distributions were also obtained for the SH product, which was found to be both vibrationally and rotationally excited. An intriguing bimodal rotational distribution in the lowest two vibrational states, v=0 and 1, has been clearly observed for the SH product, indicating that there are two distinctive dissociation mechanisms involved in the photodissociation of H2S at 157 nm excitation. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 46
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 2242-2254 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The reactions of HOCl with HCl on water clusters have been theoretically investigated. Ab initio calculations indicate that hydrogen bond and cooperative effect play an essential role in the reactions; that the reaction barrier of HOCl with cyclic (H2O)n.HCl cluster is the least at n=3 and that the ionization of HCl and HOCl on ice surfaces may not be complete but partly at very low temperatures. Two cases a and b of the model reactions are considered for detailed analysis. On the surface of ice, the barrier energies are about 4 and 6 kcal/mol for cases a and b, respectively, at the MP2//HF/6-31G(d) level, which is close to an experimental estimation. This study suggests a similar previously reported mechanism that the heterogeneous reaction of HOCl with HCl on ice is catalyzed at the stratospheric conditions through structure catalysis and hydration that enhances ion character of species. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 47
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 2235-2241 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A newly developed "interrupted creep" experiment has been used to study the physical aging of a low molecular weight polystyrene, Tg∼69 °C. The results of the new experiment are compared to those obtained from traditional "periodic creep" experiments. The interrupted creep experiment provides information about the viscosity, the recoverable creep compliance and the steady-state compliance, Js, during aging. Low molecular weight polystyrene was chosen because it exhibits a steady-state compliance that is a strong function of temperature. Aging was conducted at three temperatures, 68.2, 65.7 and 61.0 °C, using both down-jump and up-jump experiments. The behavior observed in the new experiments mirrors the behavior observed in the traditional experiments. In addition, the new experiments allow the first ever determination of how Js evolves during aging. The change of Js with aging time was calculated using the relationship between the shift factors, obtained from the recoverable creep compliance data, and the average relaxation times, obtained from the viscosity. The advantage of the new experiment is that it provides both the short-time recoverable creep compliance information and the long-time viscous flow. By combining these contributions to the creep compliance in a simple additive fashion, one can obtain a more complete picture of how the material is behaving during aging. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 48
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 2259-2269 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The effect of a patterned surface on the phase separation kinetics of a thin polymer film has been investigated using the Cahn–Hilliard–Cook model in three dimensions with the addition of a short range surface potential. We have observed pattern-induced spinodal waves perpendicular to the surface creating "checkerboard"-like composition fluctuations for a wide range of patterns used in this study. The number of such layers strongly depends on the magnitude of the thermal noise. For sufficiently thin films, where the film thickness is smaller than the spinodal wavelength, spinodal decomposition can be arrested if the surface potential and the characteristic size of the pattern are chosen accordingly, enabling the transfer of surface patterns to the film material. The kinetic pathways through which the equilibrium states are reached delicately depend on the particular pattern, its size, and the film thickness. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 49
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 4013-4024 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Exact and approximate quantum mechanical calculations of reaction probabilities and cumulative reaction probabilities have been carried out for the F+H2 reaction on the ab initio adiabatic potential energy surfaces by Stark and Werner (SW) and by Hartke, Stark, and Werner (HSW), the latter including spin–orbit corrections in the entrance channel. These data have been employed to obtain thermal rate constants for the title reaction in the temperature range 200–700 K. The exact and approximate results have been compared with experimental determinations and previous theoretical predictions. In particular, the reaction probabilities obtained on the HSW surface are found to be in very good agreement with recent calculations by Alexander et al. [J. Chem. Phys. 109, 5710 (1998)] based on the exact treatment of spin–orbit and Coriolis coupling for this system. However, the rate constants calculated on the HSW PES are systematically lower than the experimental values, which indicates that the height of the adiabatic potential energy surface is too high. Furthermore, an estimate of cross sections from the reaction probabilities calculated by Alexander et al. shows that the contribution to the low temperature rate constants from spin–orbit excited F(2P1/2) atoms through nonadiabatic channels is very small and, thus, nonadiabatic effects are not sufficient to bring the calculated rate constants to a better agreement with the experimental measurements. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 50
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 4068-4076 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The rate coefficients of reactions that occur on potential energy surfaces without a barrier often exhibit a negative temperature dependence at low temperatures. Generally, this behavior is modeled with either the Harcourt–Essen equation, k(T)=AT−m, or a "negative" activation energy, k(T)=ATm exp{ΔE/kBT}. Neither of these expressions is consistent with the Wigner threshold law. The general expression k(T)=(1+T/TW)−m∑l=0∞Al(1+T/TW)−l(T/TW)l is proposed where the relative angular momentum of the reacting species is l, TW and m are independent parameters to be extracted from the data, and the amplitude of each partial wave is Al. This expression may be approximated by k(T)=A0(1+T/TW)−m exp[(T/TW)/(1+T/TW)]. For CN+O2→ NCO+O and CO+NO the above expression reproduces the rate data, the branching ratio to the CO+NO channel, and the reactive cross section for the NCO+O channel. The rate coefficient for the NCO+O channel is given by k(cm3 s−1)=1.79×10−10(+T/21.7)−1.38{exp[(T/21.7)/(1+T/21.7)]−1}+4.62×10−12 exp[(T/21.7)/(1+T/21.7)] while for CO+NO we obtain k(cm3 s−1)=1.79×10−10(1+T/21.7)−1.38. An analytic form of the C–O bonding potential and the electric dipole–quadrupole interaction is used to show that the quantum threshold region extends up to 7 K. These results demonstrate the need of a complete quantum treatment for reactions that proceed on potential surfaces without a barrier. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 51
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 4077-4086 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The first optical investigation of the spectra of diatomic PdC has revealed that the ground state has Ω=0+, with a bond length of r0=1.712 Å. The Hund's case (a) nature of this state could not be unambiguously determined from the experimental data, but dispersed fluorescence studies to be reported in a separate publication, in combination with a comparison to theoretical calculations, demonstrate that it is the 2δ4 12σ2, 1Σ0++ state, which undergoes spin–orbit mixing with a low-lying 2δ4 12σ1 6π1, 3Π0+ state. An excited 3Σ+ state with re=1.754±0.003 Å (r0=1.758±0.002 Å) and ΔG1/2=794 cm−1 is found at T0=17 867 cm−1. Although only the Ω=1 component of this state is directly observed, the large hyperfine splitting of this state for the 105Pd 12C isotopomer implies that an unpaired electron occupies an orbital that is primarily of 5s character on Pd. Comparison to ab initio calculations identifies this state as 2δ4 12σ1 13σ1, 3Σ1+. To higher wavenumbers a number of transitions to states with Ω=0+ have been observed and rotationally analyzed. Two groups of these have been organized into band systems, despite the clear presence of homogeneous perturbations between states with Ω=0+ in the region between 22 000 and 26 000 cm−1. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 52
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 4087-4100 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: An intramolecular theory of the unusual mass-independent isotope effect for ozone formation and dissociation is described. The experiments include the enrichment factor, its dependence on the ambient pressure, the ratio of the formation rates of symmetric and asymmetric ozone isotopomers, the enrichment of ozone formed from heavily enriched oxygen isotopes, the comparison of that enrichment to that when the heavy isotopes are present in trace amounts, the isotopic exchange rate constant, and the large mass-dependent effect when individual rate constants are measured, in contrast with the mass-independent effect observed for scrambled mixtures. To explain the results it is suggested that apart from the usual symmetry number ratio of a factor of 2, the asymmetric ozone isotopomers have a larger density of reactive (coupled) quantum states, compared with that for the symmetric isotopomers (about 10%), due to being more "RRKM-like" (Rice–Ramsperger–Kessel–Marcus): Symmetry restricts the number of intramolecular resonances and coupling terms in the Hamiltonian which are responsible for making the motion increasingly chaotic and, thereby, increasingly statistical. As a result the behavior occurs regardless of whether the nuclei are bosons (16O, 18O) or fermions (17O). Two alternative mechanisms are also considered, one invoking excited electronic states and the other invoking symmetry control in the entrance channel. Arguments against each are given. An expression is given relating the mass-independent rates of the scrambled systems to the mass-dependent rates of the unscrambled ones, and the role played by a partitioning term in the latter is described. Different definitions for the enrichment factor for heavily enriched isotopic systems are also considered. In the present paper attention is focused on setting up theoretical expressions and discussing relationships. They provide a basis for future detailed calculations. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 53
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 4300-4309 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Thermodynamic and structural properties of an asymmetric electrolyte containing macroions with 60 elementary charges and monovalent counterions in aqueous solution at different concentrations have been studied by means of Monte Carlo (MC) simulations and molecular dynamics (MD) employing two different short-range potentials. The long-range Coulombic interactions were handled by using Ewald summation and the MC simulations were accelerated by a cluster-move technique, which was found to be two orders of magnitude more efficient for this system than the standard MC method. An effective repulsion was found to operate between the macroions at all concentrations. The electrostatic screening of the macroion repulsion by the counterions was stronger in the hard-sphere model as compared to a soft-sphere model. The origin of this difference arises primarily from the deeper macroion–ion potential in the former model. The results of the hard-sphere model have been compared with different more approximate theories such as the cell model solved by MC simulations, the cell model solved by the Poisson–Boltzmann (PB) equation, and the Derjaguin–Landau–Vervey–Overbeek (DLVO) theory. We have found that the cell model solved by MC simulations and combined with a charge renormalization approach is superior to the other simplified approaches and its predictions are in excellent agreement with the exact simulation results. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 54
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 4334-4342 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We present calculations of the anisotropy of the tension of interfaces separating an isotropic phase rich in a flexible polymer from a nematic phase rich in a semiflexible polymer. We find that the interfacial tension is always lower when the director is parallel to the plane of the interface than when it is perpendicular. The ratio of the tension in the perpendicular to parallel case can be quite large, of order 5 or so, depending on the strength of the nematic interactions. We also find that the interfacial width is always lower in the parallel case even though the tension is lower; this is because the orientational density prefers parallel alignment of chains at the interface. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 55
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 1501-1510 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We compute the melting curve of n-octane using Molecular Dynamics simulations with a realistic all-atom molecular model. Thermodynamic integration methods are used to calculate the free energy of the system in both the crystalline solid and isotropic liquid phases. The Gibbs–Duhem integration procedure is used to calculate the melting curve, starting with an initial point obtained from the free energy calculations. The calculations yield quantitatively accurate results: in the pressure range of 0–100 MPa, the calculated melting curve deviates by only 3 K from the experimental curve. This deviation falls just within the range of uncertainty of the calculations. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 56
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 1511-1519 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We develop the average Hamiltonian theory of a class of symmetrical radio-frequency pulse sequences in the NMR of rotating solids. Theorems are presented which allow one to predict the elimination of many average Hamiltonian terms, without detailed calculation. These results are applied to the problem of heteronuclear decoupling in the presence of rapid magic angle spinning. We present sequences which minimize the number of heteronuclear terms at the same time as recoupling the homonuclear interactions of the irradiated spins. The performance of the new sequences is tested on 13C labeled calcium formate. Experimental measurements of double-quantum 1H excitation indicate a relationship between good heteronuclear decoupling of the observed spin species and efficient recoupling of the irradiated spin species. The heteronuclear decoupling performance of the new sequences is significantly better than that obtained with an unmodulated radio-frequency field. The decoupling performance is improved further by breaking the pulse sequence symmetry in a controlled fashion. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 57
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3349-3356 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We revisit the far from equilibrium escape problem across a fluctuating potential barrier that is driven by asymmetric, unbiased dichotomous noise. Our closed analytical solution for arbitrary noise strengths reveals new aspects of the so-called "resonant-activation" effect and leads to interesting implications regarding far from equilibrium or externally controlled chemical reaction processes. Specifically, a genuine asymmetry-induced variant of resonant activation within the constant intensity scaling scheme is discovered, and a new possibility to manipulate reaction rates and yields, as well as the balance between reactants and products, is put forward. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 58
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3357-3364 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The performance of current density functionals is analyzed in detail for the electric field gradients (EFG) of hydrogen chloride and copper chloride by comparison with ab initio methods and available experimental data. The range of density functionals applied shows good agreement with coupled cluster H and Cl field gradients for HCl, as has been demonstrated previously for other main-group element containing compounds. However, the performance of most density functionals is very poor for the Cu EFG in CuCl (EFG for Cu -0.44 a.u. at the coupled-cluster singles and doubles with perturbative triples [CCSD(T)] level, compared to, e.g., +0.54 a.u. at the B-LYP level). Only the "half-and-half" hybrid functionals give field gradients with the correct sign. The reason for the poor performance of the density functional theory is analyzed in detail comparing density functional with ab initio total electronic densities ρ(r). Due to the conservation of the number of particles, a change in the valence part of the electron density can lead to changes in the core part of the density. Errors in valence electronic properties like the dipole moment and in core properties like the Cu and Cl EFGs may therefore be connected. In fact the errors in both properties show a distinct linear relationship, indicating that if the dipole moment is correctly described by density functionals, the Cu and Cl EFGs may be accurate as well. Furthermore, at the atomic level, electric field gradients are described with reasonable accuracy by current density functionals as calculations for the Cu 2P excited state and the Cu2+ 2D ground state show. A comparison between the different density functionals shows that the incorrect behavior of the electronic density appears to be mainly due to defects in the exchange part of the functional.© 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 59
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 1580-1586 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Theoretical expressions for the ultrasonically induced birefringence of liquids are obtained in the frame work of de Gennes' phenomenological theory. The intensity and frequency dependence of ultrasonically induced birefringence in the isotropic phase of p-n-pentyl p′-cyanobiphenyl (5CB) was measured in order to examine the usefulness of birefringence measurements for investigating dynamical properties liquids. The observed birefringence was proportional to the square root of ultrasonic intensity. The birefringence divided by the square root of ultrasonic intensity increases with increasing frequency and appears to saturate when the ultrasonic frequency approaches the relaxation frequency of molecular reorientation. The observed values of birefringence were reproduced satisfactorily by the expression derived in this paper. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 60
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 1592-1594 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The noisy dynamic behavior of a surface catalytic reaction model to describe the oxidation of carbon monoxide is investigated when the control parameter is perturbed by external noise near a supercritical Hopf bifurcation point. Noise induced coherent oscillation (NICO) is observed and the NICO strength goes through two maxima with the increment of the noise intensity D from zero, characteristic of the occurrence of stochastic multiresonance without external signal. The frequency of the NICO also increases with the increment of D. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 61
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 1595-1607 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The structural, dynamical, and electronic properties of solid HBr at high pressure are investigated using the ab initio constant pressure molecular dynamics method. A detailed analysis of the orientational distribution, and the reorientational and vibrational dynamics of the disordered phase I at ambient temperature showed that this phase can be described as a rotator phase with fluctuating hydrogen bonds up to pressures well over 10 GPa. We predict that the disorder at higher densities leads to cooperative proton-transfer dynamics. The approach to hydrogen-bond symmetrization is studied in phase I and the high pressure ordered phase III. The simulation results for phase III also indicate that this phase develops dielectric instabilities at high density. At pressures over 40 GPa we observe spontaneous formation of H2 with rearrangement of the Br lattice from fcc to hcp. The chemical reactivity is rationalized in terms of the electronic structure under conditions of near symmetrical hydrogen bonding. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 62
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 1608-1614 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The effect of attractive interactions on the behavior of polymers between surfaces is studied using Monte Carlo simulations. The molecules are modeled as fused sphere freely rotating chains with fixed bond lengths and bond angles; wall–fluid and fluid–fluid site–site interaction potentials are of the hard sphere plus Yukawa form. For athermal chains the density at the surface (relative to the bulk) is depleted at low densities and enhanced at high densities. The introduction of a fluid–fluid attraction causes a reduction of site density at the surface, and an introduction of a wall–fluid attraction causes an enhancement of site density at the surface, compared to when these interactions are absent. When the wall–fluid and fluid–fluid attractions are of comparable strength, however, the depletion mechanism due to the fluid–fluid attraction dominates. The center of mass profiles show the same trends as the site density profiles. Near the surface, the parallel and the perpendicular components of chain dimensions are different, which is explained in terms of a reorientation of chains. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 63
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 1615-1627 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The dynamical properties of an oscillating tip–cantilever system are now widely used in the field of scanning force microscopy. The aim of the present work is to get analytical expressions describing the nonlinear dynamical properties of the oscillator in noncontact and intermittent contact situations in the tapping mode. Three situations are investigated: the pure attractive interaction, the pure repulsive interaction, and a mixing of the two. The analytical solutions obtained allow general trends to be extracted: the noncontact and the intermittent contact show a very discriminate variation of the phase. Therefore the measurement of the phase becomes a simple way to identify whether or not the tip touches the surface during the oscillating period. It is also found that the key parameter governing the structure of the dynamical properties is the product of the quality factor by a reduced stiffness. In the attractive regime, the reduced stiffness is the ratio of an attractive effective stiffness and the cantilever one. In the repulsive regime, the reduced stiffness is the ratio between the contact stiffness and the cantilever one. The quality factor plays an important role. For large values of the quality factor; it is predicted that a pure topography can be obtained whatever the value of the contact stiffness. For a smaller quality factor, the oscillator becomes more sensitive to change of the local mechanical properties. As a direct consequence, varying the quality factor, for example with a vacuum chamber, would be a very interesting way to investigate soft materials either to access topographic information or nanomechanical properties. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 64
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3468-3478 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Inner shell electron energy spectroscopy (ISEELS) was used to study HBS, HBO, and H3B3O3, reactive, transient species generated in situ. The reaction of H2S with crystalline boron in a quartz tube was used to produce thioborine (HBS) at ∼1100 °C, and borine (HBO) at ∼1200 °C. The reaction of H2O vapor with crystalline boron in a quartz tube at ∼1200 °C was used to produce boroxine (H3B3O3). These species were identified from their inner shell excitation spectra and mass spectrometry. The B 1s, S 2s, and S 2p ISEEL spectra of HBS, and the B 1s and O 1s spectra of HBO and H3B3O3 are reported and analyzed with the help of GSCF3 ab initio calculations. A reaction scheme is proposed for the generation of HBO from the reaction of H2S and boron in a heated quartz tube. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 65
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3494-3497 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Transitions into the doubly excited Na2 1 3Σg− state have been analyzed using near-dissociation expansions (NDE) to represent the vibrational energies and inertial rotational constants, while the centrifugal distortion constants were held fixed at "mechanically consistent" values calculated from the Rydberg–Klein–Rees (RKR) potential implied by those G(v) and Bv functions. The input data cover the range v=0 to 57 and N up to 47, and the fit yields vD=61.41(±0.10) and D0=3385.70(±0.2) cm−1. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 66
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3508-3516 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Time-independent quantum scattering calculations have been performed to study the H+CH4→H2+CH3 reaction, using the analytic potential-energy surface developed by Jordan and Gilbert. A rotating bond umbrella (RBU) approximation with the implementation of a guided spectral transform subspace iteration technique has been applied together with a log-derivative method in hyperspherical coordinates. A single sector hyperspherical projection method was used to apply the boundary conditions to extract the S matrix at a large hyperradius. The results show that the H+CH4→H2+CH3 reaction occurs via a direct mechanism. The tunneling effect is pronounced, while there is little recrossing. Vibrational excitation of the C–H stretch and/or the H–CH3 bending modes of CH4 significantly enhance the reactivity. Exciting the umbrella mode of CH4 also enhance the reactivity, although less efficiently. The calculated thermal rate constants are larger than the experimental ones. However, good agreement has been obtained by including a barrier height correction of the potential function to make it agree with ab initio results. Finally, vibrational and rotational distributions of the reaction products are discussed in detail. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 67
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3517-3525 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We report experiments that investigate the influence of long-range attractive forces on collisional energy loss from highly vibrationally excited molecules. State-resolved studies of energy transfer from highly vibrationally excited pyridine (μ=2.2 D) to water (μ=1.8 D) in a low-pressure environment at 298 K have been performed using high-resolution transient absorption spectroscopy of water at λ(approximate)2.7 μm. Pyridine in its ground electronic state with 37 900 cm−1 of vibrational energy was prepared by absorption of pulsed ultraviolet light (λ=266 nm) to the S1 state, followed by rapid internal conversion to the S0 state. Collisions between vibrationally excited pyridine and water that result in rotational and translational excitation of the ground vibrationless state of H2O (000) were investigated by monitoring the populations of individual rotational states of H2O (000) at short times following pyridine excitation. The infrared probe of water was the highly allowed asymmetric stretching (000→001) transition. The nascent distribution of rotationally excited H2O (000) states is well described by a thermal distribution with a rotational temperature of Trot=770±80 K. Doppler-broadened transient linewidth measurements yield the velocity distributions of the recoiling H2O (000) molecules that correspond to center-of-mass translational temperatures of Ttrans∼515 K for all water rotational states investigated. Additionally, rate constants for energy gain in individual water states were determined, yielding an integrated rate constant of k2int=1.1×10−11 cm3 mol−1 s−1 for the appearance of H2O (000) with Erot=1000–2000 cm−1. These results are compared with previous relaxation studies of excited pyrazine (μ=0 D) with water and of excited pyridine with CO2 (μ=0 D), and the influence of electrostatic attraction on the relaxation dynamics is discussed. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 68
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We study theoretically the generation of coherent, anharmonic phonon-polariton responses through impulsive stimulated Raman scattering with intense, crossed ultrafast excitation pulses. We find that the refractive index appears modulated at the stimulated scattering wave vector and the corresponding phonon-polariton frequency, and, due to anharmonicity, at stimulated scattering wave vector overtones and their corresponding frequencies. A realistic model of the soft lattice vibrational mode of the ferroelectric crystal lithium tantalate is considered in detail. Specific predictions for the magnitudes of different wave vector overtone contributions to the lattice displacement are made compared to experimental observations of anharmonic lattice responses. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 69
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3548-3558 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Highly monochromatized electrons (with energy distributions of less than 30 meV FWHM) are used in a crossed beam experiments to investigate electron attachment to oxygen clusters (O2)n at electron energies from approximately zero eV up to several eV. At energies close to zero the attachment cross section for the reaction (O2)n+e→(O2)m− (for m=1, 2, and 3) rises strongly with decreasing electron energy compatible with s-wave electron capture to (O2)n. Peaks in the oxygen attachment cross sections present at higher energies ((approximate)80 meV, 193 meV, 302 meV) can be ascribed to vibrational levels of the anion populated by attachment of an electron to a single oxygen molecule within the target cluster via a direct Franck–Condon transition from the ground vibrational state v=0 to a vibrational excited state v′=7,8,9,... of the anion produced. The vibrational structures observed here for the first time can be quantitatively accounted for by model calculations using a microscopic model to examine the attachment of an electron to an oxygen molecule inside a cluster. This involves (i) molecular dynamics simulations to calculate the structure of neutral clusters prior to the attachment process and (ii) calculation of the solvation energy of an oxygen anion in the cluster from the electrostatic polarization of the molecules of the cluster. The occurrence of this polarization energy at the surface of larger clusters explains the appearance of an s-wave capturing cross section at 0 eV and the slightly smaller spacings (compared to the monomer case) between the peaks at finite energy, as observed experimentally. The relative transition probabilities from the ground state of the neutral oxygen molecule to the different vibrational levels of the anion are obtained by calculating the corresponding Franck–Condon factors thereby resulting in a reasonable theoretical fit to the observed yields of negatively charged oxygen molecules and clusters. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 70
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3581-3589 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Umbrella sampling Monte Carlo simulations are used to calculate free energy barriers to homogeneous liquid–vapor nucleation in the superheated Lennard-Jones fluid. The calculated free energy barriers decrease with increased superheating and vanish at the spinodal curve. A statistical geometric analysis reveals the existence of two types of voids: Small interstitial cavities, which are present even in the equilibrium liquid, and much larger cavities that develop as the system climbs the nucleation free energy barrier. The geometric analysis also shows that the average cavity size within the superheated liquid is a function of density but not of temperature. The critical nucleus for the liquid–vapor transition is found to be a large system-spanning cavity that grows as the free energy barrier is traversed. The weblike cavity is nonspherical at all superheatings studied here, suggesting a phenomenological picture quite different from that of classical nucleation theory. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 71
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3612-3615 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: High-resolution Stark effect measurements on the S1←S0(ππ*) origin of cis-free base isobacteriochlorin in single crystals of n-octane at 5 K are reported. The spectral splittings of the band at 15 822 cm−1 are linearly dependent on the applied electric field. The change in dipole moment (Δμ) was found to be 1.32 D and is parallel to the crystal's b-axis. This band blueshifted as the polarity of the solvents at room temperature was increased, which implies that Δμ is negative. To rationalize the large magnitudes and opposite signs of the cis and trans tautomers' Δμ values, we propose a simple valence-bond model based on ionic resonance structures. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 72
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 1784-1785 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The relative mixing coefficients of the zero-order 1B1(n,0,0) vibrational levels present in the hybrid 1A2–1B1 wave functions are estimated according to the observed Franck–Condon patterns in dispersed fluorescence spectra. Non-Condon effects and spin–orbit coupling have been ignored in the treatment. The data cover nearly 50 cold vibronic bands in the 32 895–34 040 cm−1 region in addition to 9 vibronic bands in the 32 185–32 559 cm−1 region. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 73
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3668-3674 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We study the drift mobility of a molecular polaron in the presence of an external applied field and Coulomb traps. The model is based on one previously developed for geminate recombination of photogenerated charge carriers. It is shown that the unusual combination of Poole–Frenkel-like field dependence and non-Arrhenius temperature dependence of the mobility, measured experimentally in molecular films, is well reproduced by this model. Our key result is that this nearly universal experimental behavior of the mobility arises from competition between rates of polaron trapping and release from a very low density of Coulomb traps. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 74
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3675-3678 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: It is known that the presence of cations like Ca++ or Pb++ in the water subphase alters the pressure-area isotherms for fatty acid monolayers. The corresponding lattice constant changes have been studied using x-ray diffraction. Reflection-absorption spectroscopy has been used to probe the chemical composition of the film. We report on the first measurements of the time evolution of the shear viscosity of arachidic acid monolayers in the presence of Ca++ ions in the subphase. We find that the introduction of Ca++ ions to the water subphase results in an increase of the film's viscosity by at least three orders of magnitude. This increase occurs in three distinct stages. First, there is a rapid change in the viscosity of up to one order of magnitude. This is followed by two periods, with very different time constants, of a relatively slow increase in the viscosity over the next 10 or more hours. The corresponding time constants for this rise decrease as either the subphase pH or Ca++ concentration is increased. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 75
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3679-3695 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: In the interaction of low energy F2 with Si(100) at 250 K, a dissociative chemisorption mechanism called atom abstraction is identified in which only one of the F atoms is adsorbed while the other F atom is scattered into the gas phase. The dynamics of atom abstraction are characterized via time-of-flight measurements of the scattered F atoms. The F atoms are translationally hyperthermal but only carry a small fraction (∼3%) of the tremendous exothermicity of the reaction. The angular distribution of F atoms is unusually broad for the product of an exothermic reaction. These results suggest an "attractive" interaction potential between F2 and the Si dangling bond with a transition state that is not constrained geometrically. These results are in disagreement with the results of theoretical investigations implying that the available potential energy surfaces are inadequate to describe the dynamics of this gas–surface interaction. In addition to single atom abstraction, two atom adsorption, a mechanism analogous to classic dissociative chemisorption in which both F atoms are adsorbed onto the surface, is also observed. The absolute probability of the three scattering channels (single atom abstraction, two atom adsorption, and unreactive scattering) for an incident F2 are determined as a function of F2 exposure. The fluorine coverage is determined by integrating the reaction probabilities over F2 exposure, and the reaction probabilities are recast as a function of fluorine coverage. Two atom adsorption is the dominant channel [P2=0.83±0.03(95%, N=9)] in the limit of zero coverage and decays monotonically to zero. Single atom abstraction is the minor channel (P1=0.13±0.03) at low coverage but increases to a maximum (P1=0.35±0.08) at about 0.5 monolayer (ML) coverage before decaying to zero. The reaction ceases at 0.94±0.11(95%, N=9) ML. Thermal desorption and helium diffraction confirm that the dangling bonds are the abstraction and adsorption sites. No Si lattice bonds are broken, in contrast to speculation by other investigators that the reaction exothermicity causes lattice disorder. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 76
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3714-3719 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The dissociative photoionization channels of gaseous Si(CH3)Cl3 and ion desorption mechanisms of solid-state analogs following valence-level excitation have been investigated by means of photoionization mass spectroscopy, threshold photoelectron spectroscopy (TPES), and photon-stimulated ion desorption (PSID) using synchroton radiation. The adiabatic ionization threshold of the parent molecular ion was determined to be 11.18 eV, consistent with the value of 11.16 eV obtained from the TPES spectrum. An energy shift ∼0.8 eV toward lower binding energies for the orbitals of solid Si(CH3)Cl3 with respect to the gas phase values was observed. Two thresholds at 14.97 and 17.51 eV in the CH3+ photoionization efficiency spectrum are probably associated with the ionization of 2e″ and 11a1 orbitals, respectively. The H+ desorption threshold at 20.1 eV in the PSID spectrum may be attributed to the excitation of C 2s electron correlation states to the unoccupied states. The Cl+ desorption threshold at 19.9 eV is likely initiated by an Auger-stimulated desorption process.© 1999 American Institute of Physics. [S0021-9606(99)70731-2]
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 77
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3720-3727 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A study of the reorientational segmental dynamics in supercooled poly(vinyl acetate) is presented, yielding detailed information about geometry and time scale of the motion close to the glass transition. The geometry information is derived from systematic variation of the evolution time in 13C 2D echo NMR measurements. The dynamics can be described as a superposition of angular jumps of approximately 10° and rotational diffusional processes. Both processes are related to the macroscopic α-relaxation. On the time scale of one jump process the orientation of a segment changes by about 2° via small step diffusion (〈0.6°). Furthermore the temperature dependence of this reorientatinal scenario is analyzed within the limits imposed by the experiment. All results are compared with previous 2H 2D NMR measurements on low-molecular glass formers. In both cases the loss of correlation, as described by conventional correlation times, results from a sequence of many distinct reorientational steps. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 78
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3744-3752 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: In this paper we complete the study of the phase diagram and conformational states of a stiff homopolymer. It is known that folding of a sufficiently stiff chain results in formation of a torus. We find that the phase diagram obtained from the Gaussian variational treatment actually contains not one, but several distinct toroidal states distinguished by the winding number. Such states are separated by first order transition curves terminating in critical points at low values of the stiffness. These findings are further supported by the off-lattice Monte Carlo simulation. Moreover, the simulation shows that the kinetics of folding of a stiff chain passes through various metastable states corresponding to hairpin conformations with abrupt U-turns. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 79
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3761-3768 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Gel-type electrolytes based on fluorinated polymers are of interest for electrochemical devices. We present a 7Li–13C solid-state NMR and modulated differential scanning calorimetry (MDSC) study of gel electrolytes based on a copolymer poly(vinylidene fluoride) (PVdF)–hexafluoropropylene (HFP) activated with a nonaqueous solution ethylene carbonate (EC)–propylene carbonate (PC)–LiN(CF3SO2)2. We show that the narrowing of the Li lineshape is decoupled from the glass transition. The behavior of the longitudinal relaxation times, T1, confirms that the host polymer matrix simply behaves like a quasiinert cage for the solution. These results are confirmed by 13C NMR at the magic angle (MAS) data, which show that the presence of the polymer does not significantly affect the chemical shift changes induced in the EC/PC carbons by the imide salt. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 80
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3572-3580 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We study, from first principles, structural, electronic, and bonding properties of liquid water. Our system is twice as large as that used in previous ab initio simulations and our computed structural properties are in good agreement with the most recent neutron scattering experiments. Moreover, the use of a novel technique, based on the generation of maximally localized Wannier functions, allowed us to describe the molecular charge distribution and the polarization effects in liquid water with a degree of accuracy not previously possible. We find that, in the liquid phase, the water molecule dipole moment has a broad distribution around an average value of about 3.0 D. This value is 60% higher than that of the gas phase and significantly larger than most previous estimates. A considerable increase is also observed in the magnitude of the average eigenvalues of the quadrupole moment tensor. We also find that the anisotropy of the electronic charge distribution of the water molecule is reduced in the liquid. The relevance of these results for current modeling of liquid water is discussed. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 81
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3769-3770 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We examine recently obtained expressions for the reversible work required to form a noncritical nucleus in a metastable vapor. We demonstrate that the expression obtained in by Debenedetti and Reiss [J. Chem. Phys. 108, 5498 (1998)] is identical to that in by Nishioka and Kusaka [J. Chem. Phys. 96, 5370 (1992)], thereby resolving the apparent contradiction between these two papers. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 82
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 2853-2856 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We study the dynamics in optical collisions of Na with Ne, Ar, Kr, and Xe in a differential scattering experiment. We report the observation of nonadiabatic transitions in the excited collisional quasimolecule based on measurements of the population ratio of the Na(3p)2P1/2 and 2P3/2 fine-structure levels. Comparison with theoretical results shows a generally very good agreement over the range of collision energies (0.01–0.3 eV) scanned in our experiment, using the best available potentials. For the heavier rare-gas systems a strong influence of the BΣ–AΠ crossing on the population ratios is observed. We further extract a universal function for the nonadiabatic transition probability for these systems. In the thermal energy range, our results are in good qualitative agreement with data from gas phase optical collision experiments. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 83
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 2857-2860 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The chemical dynamics to form cyanopropyne, CH3CCCN (X 1A1), and cyanoallene, H2CCCHCN (X 1A′), via the neutral–neutral reaction of the cyano radical, CN (X 2Σ+), with methylacetylene, CH3CCH (X 1A1), is investigated under single collision conditions in a crossed molecular beam experiment at a collision energy of 24.7 kJ mol−1. The laboratory angular distribution and time-of-flight spectra of the C4H3N products are recorded at m/e=65, 64, 63, and 62. The reaction of d3-methylacetylene, CD3CCH (X 1A1), with CN radicals yields reactive scattering signal at m/e=68 and m/e=67 demonstrating that two distinct H(D) atom loss channels are open. Forward-convolution fitting of the laboratory data reveal that the reaction dynamics are indirect and governed by an initial attack of the CN radical to the π electron density of the β carbon atom of the methylacetylene molecule to form a long lived CH3CCHCN collision complex. The latter decomposes via two channels, i.e., H atom loss from the CH3 group to yield cyanoallene, and H atom loss from the acetylenic carbon atom to form cyanopropyne. The explicit identification of the CN vs H exchange channel and two distinct product isomers cyanoallene and cyanopropyne strongly suggests the title reaction as a potential route to form these isomers in dark molecular clouds, the outflow of dying carbon stars, hot molecular cores, as well as the atmosphere of hydrocarbon rich planets and satellites such as the Saturnian moon Titan. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 84
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 2878-2888 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A time-dependent density-functional theory for systems in periodic external potentials in time is formulated on the assumption of the existence of the Floquet states from the quasienergy viewpoint. Coupling strength integration, which connects a noninteracting system with an interacting system, is introduced by using the time-dependent Hellmann–Feynman theorem. Coupled perturbed time-dependent Kohn–Sham equations are derived from the variational condition to the quasienergy functional with respect to parameters. Explicit expressions for frequency-dependent polarizability and first hyperpolarizability are given by the quasienergy derivative method. Excitation energies and transition moments are defined from poles and residues of frequency-dependent polarizabilities, respectively. In contrast to the previous theory, our formulation has the following three advantages: (1) The time-dependent exchange-correlation potential is defined by the functional derivative of the exchange-correlation quasienergy. (2) The formal expression for frequency-dependent polarizability, which corresponds to the exact sumover-states expression, can be obtained. (3) Explicit expressions for response properties which satisfy the 2n+1 rule can be automatically obtained. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 85
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 2900-2909 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We present analytical calculations of the electronic spin–orbit interaction contribution to nuclear magnetic shielding tensors using linear and quadratic response theory. The effects of the Fermi contact and the spin-dipole interactions with both the one- and two-electron spin–orbit Hamiltonians, included as first-order perturbations, are studied for the H2X (X=O, S, Se, and Te), HX (X=F, Cl, Br, and I), and CH3X (X=F, Cl, Br, and I) systems using nonrelativistic multiconfiguration self-consistent field reference states. We also present the first correlated study of the spin–orbit-induced contributions to shielding tensors arising from the magnetic field dependence of the spin–orbit Hamiltonian. While the terms usually considered are formally calculated using third-order perturbation theory, the magnetic-field dependent spin-orbit Hamiltonian requires a second-order calculation only. For the hydrogen chalcogenides, we show that contributions often neglected in studies of spin–orbit effects on nuclear shieldings, the spin-dipole coupling mechanism and the coupling of the two-electron spin–orbit Hamiltonian to the Fermi-contact operator, are important for the spin–orbit effect on the heavy-atom shielding, adding up to about half the value of the one-electron spin–orbit interaction with the Fermi-contact contribution. Whereas the second-order spin-orbit-induced shieldings of light ligands are small, the effect is larger for the heavy nuclei themselves and of opposite sign compared to the third-order contribution. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 86
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 2392-2400 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The Peierls–Hubbard model applied to N-membered ring-shaped molecules is investigated numerically and analytically. The bond configurations minimizing the total energy at half-filling of the electronic states are determined by a self-consistent method for N≤8 in a wide range of the electron–lattice and electron–electron coupling parameters. In the even-N case, only dimerized and homogeneous configurations have been found to be stable. Odd-N rings show three types of bond configurations depending on the coupling parameters. Two of these configurations have reflection symmetry whereas the third one is irregular.© 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 87
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 2401-2406 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A new semiclassical decoupling procedure for rotational projection states in rovibrationally inelastic atom-diatom and diatom-diatom collisions is developed. Computed vibrational self-relaxation rate constants for para-H2 and ortho-H2 are in good quantitative agreement (within a factor of 1.5, except for the lowest temperatures) with experimental data over the investigated temperature range 50–2000 K. This allows us to hope that also more detailed (nonmeasured) rate constants for rovibrational state-to-state transitions in molecular hydrogen, calculated by our new model, are sufficiently accurate for astrophysical applications. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 88
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 2407-2413 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The Kr2 interaction potential is studied by ab initio calculations using several large basis sets containing high polarization functions and/or bond functions. It is shown that the addition of bond functions results in a dramatic improvement for the convergence of the calculated interaction energies. At the frozen-core MP4 level, the large atomic basis set such as [9s7p4d3f2g] recovered less than 75% of the experimental well depth. In contrast, the bond function basis set such as [9s7p4d3f]-{3s3p2d1f} produced a well depth of 617 μhartrees, over 99% of the experimental well depth. The frozen-core MP4 calculation appears to overestimate the well depth by about 25 μhartrees as compared to the calculation at the CCSD(T) level. On the other hand, the inclusion of core electron correlation at the MP4 level may contribute 13 μhartrees to the well depth. Beyond the potential minimum, the use of bond functions consistently gives significant improvement in the calculated potential from the highly repulsive wall to the attractive tail region. Final remarks are made about the counterpoise method and the use of bond functions. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 89
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 2414-2422 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The kinetics of fluorescence quenching by reversible excimer formation has been studied theoretically on the basis of generalized, non-Markovian rate equations derived from a diffusion-kinetic hierarchy approach in the low-reactant density limit. It is demonstrated that, in contrast to the case of reversible excitation transfer [W. Naumann, J. Chem. Phys. 110, 3926 (1999)], compact rate kernel expressions can be derived not only for contact encounters but also for more realistic, longer-range reactivities. Given as functionals of so-called phenomenological excimer formation and dissociation coefficients, the rate kernel expressions allow a critical assessment of approximations based on time-scale separation arguments. An effective excimer formation coefficient is defined, which leads to simple and physically transparent formulas for the Laplace transforms of the excited monomer and excimer concentrations. The effect of the back reaction on the total fluorescence yield is discussed. The study also includes a critical comparison to analogous results obtained for the case of reversible energy transfer quenching. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 90
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 2423-2435 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: This paper considers the practical utility of quantum fluid dynamics (QFD) whereby the time-dependent Schrödinger's equation is transformed to observing the dynamics of an equivalent "gas continuum." The density and velocity of this equivalent gas continuum are respectively the probability density and the gradient of the phase of the wave function. The numerical implementation of the QFD equations is carried out within the Lagrangian approach, which transforms the solution of Schrödinger's equation into following the trajectories of a set of mass points, i.e., subparticles, obtained by discretization of the continuum equations. The quantum dynamics of the subparticles which arise in the present formalism through numerical discretization are coupled by the density and the quantum potential. Numerical illustrations are performed for photodissociation of NOCl and NO2 treated as two-dimensional models. The dissociation cross sections σ(ω) are evaluated in the dramatically short CPU times of 33 s for NOCl and 40 s for NO2 on a Pentium-200 MHz PC machine. The computational efficiency comes from a combination of (a) the QFD representation dealing with the near monotonic amplitude and phase as dependent variables, (b) the Lagrangian description concentrating the computation effort at all times into regions of highest probability as an optimal adaptive grid, and (c) the use of an explicit time integrator whereby the computational effort grows only linearly with the number of discrete points. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 91
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 2436-2443 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Infrared molecular beam depletion spectroscopy of small methanol and acetonitrile clusters embedded in large helium clusters has been studied in the spectral region of the CO stretch and the CH3 rock mode from 1023 to 1059 cm−1. The results are compared with the experimental spectra of the corresponding free clusters generated in adiabatic expansions and calculations based on density functional theory or empirical potential models. For methanol clusters, the two types of experimental results are the same for the dimer and trimer structure. Different isomers are found in cold helium for the tetramer and pentamer, namely a monomer and dimer attached to a cyclic trimer. For acetonitrile clusters in helium, aside from the dimer, different structures are observed. The spectra from the trimer to the hexamer are dominated by structures which contain the antiparallel dimer as building block with D2d symmetry for the tetramer. They do not correspond to the minimum configurations observed for the free clusters. The fragmentation of the two cluster groups in helium droplets by electron impact ionization is discussed. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 92
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3051-3057 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The nuclear wave packet dynamics in the potential well of a bound molecule can be controlled by an intense infrared (IR)-laser pulse. The phase of the nuclear wave packet motion is shown to depend on the phase of the laser field and the initial orientation of the molecule. We demonstrate, for diatomic heteronuclear molecules, that these spatial effects can be used to control the angular distribution of photofragments by selective dissociation of molecules with a given initial orientation from a sample of randomly oriented molecules. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 93
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3077-3082 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Three methods for two-dimensional correlation nuclear magnetic resonance spectroscopy at zero field are discussed. All three involve coherence transfer via longitudinal polarization, double quantum coherence, or both in parallel. The double quantum pulse sequences exploit the spinor property of spin states. These sequences have been applied to connected Δm=1 transitions, as well as for the indirect detection of forbidden or nearly forbidden Δm〉1 transitions. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 94
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3083-3094 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Collective excitations in liquid water are investigated using the recently developed theory for dynamics of molecular liquids which is based on the interaction-site model for polyatomic fluids, the projection-operator formalism of Zwanzig and Mori, and the simple approximation scheme for memory functions. It is shown that all the essential features of collective excitations in water, reported previously by neutron-scattering experiments, molecular dynamics simulations and dielectric theories, are well reproduced by the present theory. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 95
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3070-3076 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: For the open shell van der Waals molecule, CAr, the potential energy curves (PECs) for the B 3Π and 1 5Σ− states, the B 3Π–1 5Σ− spin–orbit coupling and the B 3Π fine structure splitting are determined using multireference configuration interaction wave functions as large as ∼8 million configuration state functions. The B 3Π state is strongly bound, with De=5100 cm−1. Re(B 3Π)=3.7a0 and is considerably shorter than Re(X 3Σ−)=6.07 a0. The PEC for the repulsive 1 5Σ− state crosses that of the B 3Π state at Rx(1 5Σ−,B 3Π)=3.31a0 leading to spin–orbit induced predissociation. The B 3Π–1 5Σ− spin–orbit coupling is the result of valence-Ryberg mixing in the B 3Π state and is considerably enhanced by the heavy atom effect. The heavy atom effect is also reflected in a marked decrease in the fine structure splitting of the B 3Π state with increasing vibrational level. The implications of these results for using CAr(B 3Π) in laser induced fluorescence detection of CAr(X 3Σ−,v) are discussed. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 96
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3058-3069 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We have obtained rotationally resolved pulsed filed ionization photoelectron (PFI-PE) spectra of NO in the energy range of 9.2–16.8 eV, covering ionization transitions of NO+(X 1Σ+,v+=0–32,J+)←NO(X 2Π3/2,1/2,v″=0,J″). The PFI-PE bands for NO+(X 1Σ+,v+=6–32) obtained here represent the first rotationally resolved spectroscopic data for these states. The simulation using the Buckingham–Orr–Sichel model provides accurate molecular constants for NO+(X 1Σ+,v+=0–32), including ionization energies, vibrational constants (ωe+=2 382.997±0.122 cm−1, ωe+χe+=17.437 84±0.000 90 cm−1, ωe+ye+=0.063 209 5±3.2×10−6 cm−1, and ωe+ze+=−0.001 400 0±7.2×10−8 cm−1), and rotational constants (Be+=1.996 608±0.006 259 cm−1, αe+=0.020 103±6.3×10−5 cm−1, and γe+=−(7.22±2.26)×10−6 cm−1). For v+=0–15, the rotational branches are ΔJ=J+−J″=±1/2, ±3/2, ±5/2, ±7/2, and ±9/2, which correspond to the formation of photoelectron angular momentum states l=0, 1, 2, and 3. The ΔJ=±1/2, ±3/2, ±5/2, ±7/2, ±9/2, and ±11/2 rotational branches are observed in the spectra for v+=16–32, revealing the production of continuum photoelectron states l=0, 1, 2, 3, and 4. The maximum ΔJ value and intensities for high ΔJ rotational branches are found to generally increase as v+ is increased in the range of 0–32. This observation is attributed to an increase in inelastic cross sections for collisions between the outgoing photoelectron and the nonspherical molecular ion core as the bond distance for NO+ is increased. Thus, this observation can be taken as strong support for the electron-molecular-ion-core scattering model for angular momentum and energy exchanges in the threshold photoionization of NO. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 97
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3105-3114 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We have demonstrated that fifth-order stimulated Raman spectra of the intermolecular modes in CS2 are dominated by cascading third-order processes. Previous studies have successfully discriminated against a sequential cascading process, but did not account for parallel third-order cascades. All of our measured spectra were successfully simulated considering only cascades built directly from our measured third-order spectra. Using an appropriately chosen phase matching geometry we also measured the sequential cascade, which should exist with equal probability to the parallel cascade. When employing a phase matching geometry that provided substantial discrimination against all of the third-order cascades we were not able to measure any signal. We assign an upper limit for the true fifth-order signal of 2% of the cascaded signal. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 98
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3121-3132 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The excited state mixing effect is taken into account considering the difference spectra of dimers. Both the degenerate (homo) dimer as well as the nondegenerate (hetero) dimer are considered. Due to the higher excited state mixing with the two-exciton states in the homodimer, the excited state absorption (or the difference spectrum) can be strongly affected in comparison with the results obtained in the Heitler–London approximation. The difference spectrum of the heterodimer is influenced by two resonance effects (i) mixing of the ground state optical transitions of both monomers in the dimer and (ii) mixing of the excited state absorption of the excited monomer with the ground state optical transition in the nonexcited monomer. These effects have been tested by simulating the difference absorption spectra of the light-harvesting complex of photosystem II (LHC II) experimentally obtained with the 60 fs excitation pulses at zero delay times and various excitation wavelengths. The pairs of coupled chlorophylls a and b for simulations have been taken from the best LHC II assignment model obtained by simulating the steady-state spectra and the transient absorption at various excitation wavelengths. Qualitatively the spectral peculiarities of the difference spectra are explained by means of the resonance interpigment interactions, which are responsible for the excited state mixing. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 99
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 2490-2498 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The photoloc technique with core extraction of the nascent product laboratory speed distribution in a Wiley–McLaren time-of-flight spectrometer has been used to measure differential cross sections for the reaction H+D2→HD (v′=2, J′=0,3,5)+D at collision energies ∼1.55 eV. We find that the peak of each angular distribution shifts from complete backward scattering toward side scattering as the rotational excitation of the product increases. We found the same trend in our previous study of H+D2→HD (v′=1, J′=1,5,8)+D at ∼1.70 eV. We conclude that the same type of correlation exists between impact parameter and rotational quantum number in both product vibrational manifolds. Further analysis of the HD (v′=2, J′) differential cross section data reveals, however, a clear tendency of this vibrational manifold to scatter sideways at lower J′ than HD(v′=1, J′). Within the framework of a line-of-centers model with nearly elastic specular scattering, this result implies that smaller impact parameters lead to more vibrationally excited products. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
  • 100
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 2499-2506 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Three high-level correlated ab initio studies have recently been performed on the electronic absorption spectrum of free base porphin (FBP), but significant differences between the various assignments of the low-lying bands remain. In view of the importance of FBP as the basic building block of the porphyrins, further reliable results are evidently required and are provided here, using time-dependent density functional theory (TDDFT). Our results strongly support the recent CASPT2 interpretation which is consistent with the traditional interpretation, stating that the intense B band (or Soret band) is due to the two close-lying excitations 2 1B2u and 2 1B3u. As in the CASPT2 paper, we attribute all low-lying bands to pairs of 1B2u–1B3u excitations. The interpretation of the combined B–N band system is discussed in some detail. The effects of basis set, geometry, and choice of exchange-correlation potential are considered as well. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
Close ⊗
This website uses cookies and the analysis tool Matomo. More information can be found here...