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  • Oxford University Press  (101.682)
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  • 1
    Publikationsdatum: 2020-11-20
    Beschreibung: Siwi caldera, in the Vanuatu arc (Tanna island), is a rare volcanic complex where both persistent eruptive activity (Yasur volcano)and rapid block resurgence (Yenkahe horst) can be investigated simultaneously during a post-caldera stage. Here we provide new constraints on the feeding system of this volcanic complex, based on a detailed study of the petrology, geochemistry and volatile content of Yasur^Siwi bulk-rocks and melt inclusions, combined with measurements of the chemical composition and mass fluxes of Yasur volcanic gases. Major and trace element analyses of Yasur^ Siwi volcanic rocks, together with literature data for other volcanic centers, point to a single magmatic series and possibly long-lived feeding of Tanna volcanism by a homogeneous arc basalt. Olivine-hosted melt inclusions show that the parental basaltic magma, which produces basaltic-trachyandesites to trachyandesites by 50^70% crystal fractionation, is moderately enriched in volatiles ( 1wt % H2O, 0·1wt % S and 0·055 wt % Cl). The basaltic-trachyandesite magma, emplaced at between 4^5 km depth and the surface, preserves a high temperature (1107 158C) and constant H2O content ( 1wt %) until very shallow depths, where it degasses extensively and crystallizes. These conditions, maintained over the past 1400 years of Yasur activity, require early water loss during basalt differentiation, prevalent open-system degassing, and a relatively high heat flow ( 109W). Yasur volcano releases on average 13·4 103 tons d 1 of H2O and 680 tons d 1 of SO2, but moderate amounts of CO2 (840 tons d 1), HCl (165 tons d 1), and HF (23 tons d 1). Combined with melt inclusion data, these gas outputs constrain a bulk magma degassing rate of 5 107 m3 a 1, about a half of which is due to degassing of the basaltic-trachyandesite. We compute that 25 km3 of this magma have degassed without erupting and have accumulated beneath Siwi caldera over the past 1000 years, which is one order of magnitude larger than the accumulated volume uplift of the Yenkahe resurgent block. Hence, basalt supply and gradual storage of unerupted degassed basaltictrachyandesite could easily account for (or contribute to) the Yenkahe block resurgence.
    Beschreibung: Published
    Beschreibung: 1077-1105
    Beschreibung: 2.3. TTC - Laboratori di chimica e fisica delle rocce
    Beschreibung: 2.4. TTC - Laboratori di geochimica dei fluidi
    Beschreibung: JCR Journal
    Beschreibung: restricted
    Schlagwort(e): Vanuatu arc ; Yasur ; gas fluxes ; volatiles ; melt inclusions ; resurgent block ; volcano thermal budget ; 04. Solid Earth::04.04. Geology::04.04.12. Fluid Geochemistry ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 04. Solid Earth::04.08. Volcanology::04.08.03. Magmas
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 2
    Publikationsdatum: 2020-11-26
    Beschreibung: So far, the role of appendicularians in the biogeochemical cycling of organic matter has been largely overlooked. Appendicularians represent only a fraction of total mesozooplankton biomass, however these ubiquitous zooplankters have very high filtration and growth rates compared to copepods, and produce numerous fecal pellets and filtering houses contributing to export production by aggregating small marine particles. To study their quantitative impact on biogeochemical flux, we have included this group in the biogeochemical flux model, using a recently developed ecophysiological model. One-dimensional annual simulations of the pelagic ecosystem including appendicularians were conducted with realistic surface forcing for the year 2000, using data from the DyFAMed open ocean station. The appendicularian grazing impact was generally low, but appendicularians increased detritus production by 8% and export production by 55% compared to a simulation without appendicularians. Therefore, current biogeochemical models lacking appendicularians probably under, or misestimate the detritus and export production by omitting the pathway from small-sized plankton to fast sinking detritus. Detritus production and export rates are 60% lower than the estimates from mesotrophic sites, showing that appendicularians’ role is lower but still significant in oligotrophic environments. The simulated annual export at 200 m exceeds sediment trap values by 44%, suggesting an intense degradation during the sinking of appendicularian detritus, supported by observations made at other sites. Thus, degradation and grazing of appendicularian detritus need better quantification if we are to accurately assess the role of appendicularia in export flux.
    Beschreibung: EU-FP6 project SESAME GOCE-036949
    Beschreibung: Published
    Beschreibung: 855-872
    Beschreibung: 3.7. Dinamica del clima e dell'oceano
    Beschreibung: JCR Journal
    Beschreibung: reserved
    Schlagwort(e): BFM ; zooplankton ; 03. Hydrosphere::03.01. General::03.01.01. Analytical and numerical modeling ; 03. Hydrosphere::03.01. General::03.01.07. Physical and biogeochemical interactions ; 03. Hydrosphere::03.04. Chemical and biological::03.04.01. Biogeochemical cycles ; 03. Hydrosphere::03.04. Chemical and biological::03.04.04. Ecosystems
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 3
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    Unbekannt
    Oxford University Press
    In:  EPIC3Journal of Experimental Botany, Oxford University Press, ISSN: 0022-0957
    Publikationsdatum: 2019-07-17
    Repository-Name: EPIC Alfred Wegener Institut
    Materialart: Article , isiRev
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  • 4
    Publikationsdatum: 2017-04-04
    Beschreibung: Crystal-rich lithic clasts occurring in volcanic deposits are key tools to understand processes of storage, cooling, and fractionation of magmas in pre-eruptive volcanic systems. These clasts, indeed, represent snapshots of the magma-chamber/host-rock interface before eruptions and provide information on crystallization, differentiation, and degrees of interaction between magma and wall-rocks. In this study, with the aim to shed light on magma-carbonate interaction and CO2 emission in volcanic areas, we focused on the petrology of cumulate and skarn rocks by using as case study a suite of mafic and calcite-bearing lithic clasts from the Colli Albani Volcanic District. By means of phase relations, bulk rock chemistry, phase compositions, and stable isotope data we have recognized different types of cumulates and skarns. Cumulates containing either clinopyroxene±olivine associated with Cr-bearing spinel or glass+phlogopite have been divided in primitive and differentiated, respectively. Primitive cumulates originate at the interface between a relatively primitive magma and carbonate-bearing rocks and show evidences of olivine instability (i.e. heteradcumulate texture) due to carbonate assimilation. Differentiated cumulates, characterized by Ca-rich olivines, phlogopite, and glass containing calcite, form from a differentiated magma in a system open to CaO-contamination. Skarns has been divided in exoskarns, characterized by xenomorphic texture and abundant calcite, and endoskarns, characterized by hypidiomorphic texture, Ca-Tschermak-rich mineral phases, and interstitial glass. Exoskarns formed by means of solid state reactions in a dolostone protolith whereas endoskarns crystallized at subliquidus temperature from a silicate melt that experienced exoskarns assimilation. Our study evidences that magma-carbonate interaction can not be considered a one step process exhausting just after the formation of skarn shells. Magma and carbonate rocks, when in contact, continuously interact leading to the formation of exoskarns, endoskarns, cumulates (primitive and differentiated ones), and differentiated melts. Finally, by means of oxygen and carbon isotope compositions of calcite in equilibrium with skarns, we demonstrate that carbonate assimilation represents a source of massive CO2 degassing mechanism due to the consumption of calcite and removing of CO2 during the decarbonation process.
    Beschreibung: Sapienza Universita' di Roma INGV-DPC [Project V 3.1, Colli Albani].
    Beschreibung: Published
    Beschreibung: 2307-2332
    Beschreibung: 2.3. TTC - Laboratori di chimica e fisica delle rocce
    Beschreibung: JCR Journal
    Beschreibung: reserved
    Schlagwort(e): magma/carbonate interaction ; CO2 degassing ; c umulate and skarn ; Colli Albani ; 04. Solid Earth::04.04. Geology::04.04.05. Mineralogy and petrology
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 5
    Publikationsdatum: 2017-04-04
    Beschreibung: Stromboli is known for its persistent degassing and rhythmic strombolian activity occasionally punctuated by paroxysmal eruptions. The basaltic pumice and scoria emitted during paroxysms and strombolian activity, respectively, differ in their textures, crystal contents and glass matrix compositions, which testify to distinct conditions of crystallization, degassing and magma ascent. We present here an extensive dataset on major elements and volatiles (CO2, H2O, S and Cl) in olivine-hosted melt inclusions and embayments from pyroclasts emplaced during explosive eruptions of variable magnitude. Magma saturation pressures were assessed from the dissolved amounts of H2O and CO2 taking into account the melt composition evolution. Both pressures and melt inclusion compositions indicate that (1) Ca-basaltic melts entrapped in high-Mg olivines (Fo89–90) generate Stromboli basalts through crystal fractionation, and (2) the Stromboli plumbing system can be imaged as a succession of magma ponding zones connected by dikes. The 7–10 km interval, where magmas are stored and differentiate, is periodically recharged by new magma batches, possibly ranging from Ca-basalts to basalts, with a CO2-rich gas phase. These deep recharges promote the formation of bubbly basalt blobs, which are able to intrude the shallow plumbing system (2–4 km), where CO2 gas fluxing enhances H2O loss, crystallization and generation of crystal-rich, dense, degassed magma. Chlorine partitioning into the H2O–CO2-bearing gas phase accounts for its efficient degassing (≥69%) under the open-system conditions of strombolian activity. Paroxysms, however, are generated through predominantly closed-system ascent of basaltic magma batches from the deep storage zone. In this situation crystallization is negligible and sulfur exsolution starts at ≤170 MPa. Chlorine remains dissolved in the melt until lower pressures, only 16% being lost upon eruption. Finally, we propose a continuum in explosive eruption energy, from strombolian activity to large paroxysmal events, ultimately controlled by variable pressurization of the deep feeding system associated with magma and gas recharges.
    Beschreibung: Published
    Beschreibung: 603-626
    Beschreibung: 2.3. TTC - Laboratori di chimica e fisica delle rocce
    Beschreibung: 3.5. Geologia e storia dei vulcani ed evoluzione dei magmi
    Beschreibung: JCR Journal
    Beschreibung: reserved
    Schlagwort(e): Stromboli ; melt inclusions ; magmatic volatiles ; CO2 fluxing ; magma degassing ; 04. Solid Earth::04.04. Geology::04.04.05. Mineralogy and petrology ; 04. Solid Earth::04.08. Volcanology::04.08.03. Magmas
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 6
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    Oxford University Press
    In:  EPIC3Ocean Acidification, Oxford, Oxford University Press, pp. 291-311, ISBN: 978-0-19-959109-1
    Publikationsdatum: 2014-04-15
    Repository-Name: EPIC Alfred Wegener Institut
    Materialart: Inbook , peerRev
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  • 7
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    Oxford University Press
    In:  EPIC3Journal of Plankton Research, Oxford University Press, 34(5), pp. 399-415, ISSN: 0142-7873
    Publikationsdatum: 2019-07-17
    Beschreibung: This study investigates the relationships between the spring phytoplankton community and environmental factors in the Brazil-Malvinas confluence region. Phytoplankton community composition was determined by the high performance liquid chromatography/CHEMTAX approach, complemented with microscopic examination. Abiotic factors included temperature, salinity, dissolved inorganic macronutrients (ammonium, nitrite, nitrate, phosphate and silicate), water column stability and upper mixed layer depth (UMLD). These environmental variables were reasonably informative to explain the variability of the phytoplankton communities (44% of variation explained). Cluster and canonical correspondence analyses allowed discrimination of four zones (coastal, Sub-Antarctic, tropical and intermediate zones), also identifiable in the T–S diagrams and in the nutrient spatial distribution patterns. The presence of nutrient-rich Sub-Antarctic waters was a major oceanographic feature, associated with diatoms and dinoflagellates. However, in the Sub-Antarctic zone, biomass was particularly low, probably as a result of grazing pressure, as suggested by chemical and biological indicators. In contrast, in oligotrophic tropical waters, phytoplankton was mainly composed by small nanoflagellates and cyanobacteria. A large intermediate zone was also dominated by nanoflagellates, mainly Phaeocystis antarctica, probably favored by strong water column stability. The coastal zone exhibited fairly similar conditions to those in the intermediate zone, but with deeper UMLD, a favorable condition for diatom growth. These results emphasize the importance of the properties of water masses and also biological processes such as grazing in structuring phytoplankton communities in the region.
    Repository-Name: EPIC Alfred Wegener Institut
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  • 8
    Publikationsdatum: 2022-05-25
    Beschreibung: © The Author(s), 2013. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Conservation Physiology 1 (2013): cot006, doi:10.1093/conphys/cot006.
    Beschreibung: Large whales are subjected to a variety of conservation pressures that could be better monitored and managed if physiological information could be gathered readily from free-swimming whales. However, traditional approaches to studying physiology have been impractical for large whales, because there is no routine method for capture of the largest species and there is presently no practical method of obtaining blood samples from free-swimming whales. We review the currently available techniques for gathering physiological information on large whales using a variety of non-lethal and minimally invasive (or non-invasive) sample matrices. We focus on methods that should produce information relevant to conservation physiology, e.g. measures relevant to stress physiology, reproductive status, nutritional status, immune response, health, and disease. The following four types of samples are discussed: faecal samples, respiratory samples (‘blow’), skin/blubber samples, and photographs. Faecal samples have historically been used for diet analysis but increasingly are also used for hormonal analyses, as well as for assessment of exposure to toxins, pollutants, and parasites. Blow samples contain many hormones as well as respiratory microbes, a diverse array of metabolites, and a variety of immune-related substances. Biopsy dart samples are widely used for genetic, contaminant, and fatty-acid analyses and are now being used for endocrine studies along with proteomic and transcriptomic approaches. Photographic analyses have benefited from recently developed quantitative techniques allowing assessment of skin condition, ectoparasite load, and nutritional status, along with wounds and scars from ship strikes and fishing gear entanglement. Field application of these techniques has the potential to improve our understanding of the physiology of large whales greatly, better enabling assessment of the relative impacts of many anthropogenic and ecological pressures.
    Beschreibung: This work was supported by the United States Office of Naval Research (award #N000141110435 to K.E.H., award #N000141110540 to R.M.R., and award #N0001412WX20890 to L.C.Y. and C.E.D.); the United Kingdom Natural Environmental Research Council (supporting A.J.H.); the National Center for Research Resources, a component of the United States National Institutes of Health (NIH; supporting C.E.D.); the NIH Roadmap for Medical Research (UL1 RR024146 supporting C.E.D.); The Hartwell Foundation (supporting C.E.D.) and the 2012 Marine Mammal Breath Workshop, which was funded by the National Oceanic and Atmospheric Administration’s Marine Mammal Health and Stranding Response Program.
    Schlagwort(e): Blow ; Biopsy dart ; Cetacea ; Faecal samples ; Non-invasive ; Visual health assessment
    Repository-Name: Woods Hole Open Access Server
    Materialart: Article
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  • 9
    Publikationsdatum: 2022-05-25
    Beschreibung: © 2010 The Authors. This article is distributed under the terms of the Creative Commons Attribution-Noncommercial License. The definitive version was published in ICES Journal of Marine Science: Journal du Conseil 67 (2010): 365-378, doi:10.1093/icesjms/fsp262.
    Beschreibung: A commercial acoustic system, originally designed for seafloor applications, has been adapted for studying fish with swimbladders. The towed system contains broadband acoustic channels collectively spanning the frequency range 1.7–100 kHz, with some gaps. Using a pulse-compression technique, the range resolution of the echoes is ~20 and 3 cm in the lower and upper ranges of the frequencies, respectively, allowing high-resolution imaging of patches and resolving fish near the seafloor. Measuring the swimbladder resonance at the lower frequencies eliminates major ambiguities normally associated with the interpretation of fish echo data: (i) the resonance frequency can be used to estimate the volume of the swimbladder (inferring the size of fish), and (ii) signals at the lower frequencies do not depend strongly on the orientation of the fish. At-sea studies of Atlantic herring demonstrate the potential for routine measurements of fish size and density, with significant improvements in accuracy over traditional high-frequency narrowband echosounders. The system also detected patches of scatterers, presumably zooplankton, at the higher frequencies. New techniques for quantitative use of broadband systems are presented, including broadband calibration and relating target strength and volume-scattering strength to quantities associated with broadband signal processing.
    Beschreibung: The research was supported by the US Office of Naval Research, grants number N00014-04-1-0440 and N00014-04-1-0475, NOAA/CICOR cooperative agreement NA17RJ1223, NOAA/ National Marine Fisheries Service, and the J. Seward Johnson Chair of the WHOI Academic Programs Office.
    Schlagwort(e): Acoustic scattering ; Broadband ; Echosounder ; Fish ; Resonance
    Repository-Name: Woods Hole Open Access Server
    Materialart: Article
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  • 10
    Publikationsdatum: 2022-05-25
    Beschreibung: © The Author(s), 2012. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Nucleic Acids Research 40 (2012): W82-W87, doi:10.1093/nar/gks418.
    Beschreibung: Amplicon sequencing of the hypervariable regions of the small subunit ribosomal RNA gene is a widely accepted method for identifying the members of complex bacterial communities. Several rRNA gene sequence reference databases can be used to assign taxonomic names to the sequencing reads using BLAST, USEARCH, GAST or the RDP classifier. Next-generation sequencing methods produce ample reads, but they are short, currently ∼100–450 nt (depending on the technology), as compared to the full rRNA gene of ∼1550 nt. It is important, therefore, to select the right rRNA gene region for sequencing. The primers should amplify the species of interest and the hypervariable regions should differentiate their taxonomy. Here, we introduce TaxMan: a web-based tool that trims reference sequences based on user-selected primer pairs and returns an assessment of the primer specificity by taxa. It allows interactive plotting of taxa, both amplified and missed in silico by the primers used. Additionally, using the trimmed sequences improves the speed of sequence matching algorithms. The smaller database greatly improves run times (up to 98%) and memory usage, not only of similarity searching (BLAST), but also of chimera checking (UCHIME) and of clustering the reads (UCLUST). TaxMan is available at http://www.ibi.vu.nl/programs/taxmanwww/.
    Beschreibung: University of Amsterdam under the research priority area ‘Oral Infections and Inflammation’ (to B.W.B.); National Science Foundation [NSF/BDI 0960626 to S.M.H.]; the European Union Seventh Framework Programme (FP7/ 2007-2013) under ANTIRESDEV grant agreement no 241446 (to E.Z.).
    Repository-Name: Woods Hole Open Access Server
    Materialart: Article
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  • 11
    Publikationsdatum: 2022-05-25
    Beschreibung: © The Author(s), 2013. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Briefings in Bioinformatics 15 (2014): 783-787, doi:10.1093/bib/bbt010.
    Beschreibung: The extremely high error rates reported by Keegan et al. in ‘A platform-independent method for detecting errors in metagenomic sequencing data: DRISEE’ (PLoS Comput Biol 2012;8:e1002541) for many next-generation sequencing datasets prompted us to re-examine their results. Our analysis reveals that the presence of conserved artificial sequences, e.g. Illumina adapters, and other naturally occurring sequence motifs accounts for most of the reported errors. We conclude that DRISEE reports inflated levels of sequencing error, particularly for Illumina data. Tools offered for evaluating large datasets need scrupulous review before they are implemented.
    Beschreibung: National Institutes of Health [1UH2DK083993 to M.L.S.]; National Science Foundation [BDI- 096026 to S.M.H.].
    Schlagwort(e): Next-generation sequencing ; Sequencing error ; Adapter ligation ; PCR ; Quality score
    Repository-Name: Woods Hole Open Access Server
    Materialart: Article
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  • 12
    Publikationsdatum: 2022-05-25
    Beschreibung: © The Authors, 2010. This article is distributed under the terms of the Creative Commons Attribution-Noncommercial License. The definitive version was published in Journal of Plankton Research 32 (2010): 1355-1368, doi:10.1093/plankt/fbq062.
    Beschreibung: Increasing availability and extent of biological ocean time series (from both in situ and satellite data) have helped reveal significant phenological variability of marine plankton. The extent to which the range of this variability is modified as a result of climate change is of obvious importance. Here we summarize recent research results on phenology of both phytoplankton and zooplankton. We suggest directions to better quantify and monitor future plankton phenology shifts, including (i) examining the main mode of expected future changes (ecological shifts in timing and spatial distribution to accommodate fixed environmental niches vs. evolutionary adaptation of timing controls to maintain fixed biogeography and seasonality), (ii) broader understanding of phenology at the species and community level (e.g. for zooplankton beyond Calanus and for phytoplankton beyond chlorophyll), (iii) improving and diversifying statistical metrics for indexing timing and trophic synchrony and (iv) improved consideration of spatio-temporal scales and the Lagrangian nature of plankton assemblages to separate time from space changes.
    Beschreibung: This study was supported by NSF grants to R.J.: OCE-0727033, 0815838 and 0732152. NSF grants to A.C.T.: OCE-0535386, 0815051 and 0814413. NSF grant to J.A.R.: OCE 0815336.
    Schlagwort(e): Plankton ; Phenology ; Life history ; Climate change
    Repository-Name: Woods Hole Open Access Server
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  • 13
    Publikationsdatum: 2022-05-25
    Beschreibung: © The Authors, 2010. This article is distributed under the terms of the Creative Commons Attribution-Noncommercial 2.5 License. The definitive version was published in Genome Biology and Evolution 2 (2010): 304, doi:10.1093/gbe/evq022.
    Beschreibung: Reduction of various biological processes is a hallmark of the parasitic lifestyle. Generally, the more intimate the association between parasites and hosts the stronger the parasite relies on its host's physiology for survival and reproduction. However, some systems have been held to be indispensable, for example, the core pathways of carbon metabolism that produce energy from sugars. Even the most hardened anaerobes that lack oxidative phosphorylation and the tricarboxylic acid cycle have retained glycolysis and some downstream means to generate ATP. Here we describe the deep-coverage genome resequencing of the pathogenic microsporidiian, Enterocytozoon bieneusi, which shows that this parasite has crossed this line and abandoned complete pathways for the most basic carbon metabolism. Comparing two genome sequence surveys of E. bieneusi to genomic data from four other microsporidia reveals a normal complement of 353 genes representing 30 functional pathways in E. bieneusi, except that only 2 out of 21 genes collectively involved in glycolysis, pentose phosphate, and trehalose metabolism are present. Similarly, no genes encoding proteins involved in the processing of spliceosomal introns were found. Altogether, E. bieneusi appears to have no fully functional pathway to generate ATP from glucose. Therefore, this intracellular parasite relies on transporters to import ATP from its host.
    Beschreibung: This work was supported by grants from the Canadian Institutes for Health Research (MOP-84265), the National Institutes of Health (NIH AI31788, R21 AI52792, and R21 AI064118), and the National Science Foundation (MCB- 0135272). N.C. is a Scholar of the Canadian Institute for Advanced Research and is supported by a fellowship from the Swiss National Science Foundation (NSF) (PA00P3- 124166). D.E. is supported by the Swiss NSF. P.J.K. is a Fellow of the Canadian Institute for Advanced Research and a Senior Scholar of the Michael Smith Foundation for Health Research.
    Schlagwort(e): Microsporidia ; Parasite ; Glycolysis ; Carbon metabolism ; Reduction ; Evolution
    Repository-Name: Woods Hole Open Access Server
    Materialart: Article
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  • 14
    Publikationsdatum: 2022-05-25
    Beschreibung: Author Posting. © The Authors, 2014. This article is posted here by permission of The Royal Astronomical Society for personal use, not for redistribution. The definitive version was published in Geophysical Journal International 197 (2014): 697-704, doi:10.1093/gji/ggu048.
    Beschreibung: After the 1960 M9.5 Valdivia, Chile earthquake, three types of geodetic observations were made during four time periods at nearby locations. These post-seismic observations were previously explained by post-seismic afterslip on the downdip extension of the 1960 rupture plane. In this study, we demonstrate that the post-seismic observations can be explained alternatively by volumetric viscoelastic relaxation of the asthenosphere mantle. In searching for the best-fitting viscosity model, we invert for two variables, the thickness of the elastic lithosphere, He, and the effective Maxwell decay time of the asthenosphere mantle, TM, assuming a 100-km-thick asthenosphere mantle. The best solutions to fit the observations in four sequential time periods, 1960–1964, 1960–1968, 1965–1973 and 1980–2010, each yield a similar He value of about 65 km but significantly increasing TM values of 0.7, 6, 10 and 80 yr, respectively. We calculate the corresponding viscoelastic Coulomb stress increase since 1960 on the future rupture plane of the 2010 M8.8 Maule, Chile earthquake. The calculated viscoelastic stress increase on the 2010 rupture plane varies gradually from 13.1 bars at the southern end to 0.1 bars at the northern end. In contrast, the stress increase caused by an afterslip model has a similar spatial distribution but slightly smaller values of 0.1–3.2 bars on the 2010 rupture plane.
    Beschreibung: This work was supported by a MIT/WHOI Joint Program Student Fellowship and a Graduate Student Fellowship from the WHOI Deep Ocean Exploration Institute (MD), as well as NSF Grant OCE-1141785 and a Deerbrook Foundation Award (JL).
    Schlagwort(e): Seismic cycle ; Transient deformation ; Seismicity and tectonics ; Subduction zone processes ; Dynamics: seismotectonics ; South America
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  • 15
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    Unbekannt
    Oxford University Press
    In:  EPIC3Geophysical Journal International, Oxford University Press, 193(3), pp. 1399-1414, ISSN: 0956-540X
    Publikationsdatum: 2019-07-16
    Beschreibung: The Boreas Basin is located in the Norwegian-Greenland Sea between Northeast Greenland and Svalbard. Towards the east, it is bounded by the ultraslow mid-ocean Knipovich Ridge. Here, we present a 340-km-long seismic refraction line acquired during the expedition ARK-XXIV/3 of research vessel Polarstern in 2009, using 18 ocean bottom seismometers. It crosses the central Boreas Basin from the Knipovich Ridge to the Northeast Greenland margin. Thus, the line provides the first reliable crustal structure information of this basin. In addition, the gravity data acquired parallel to the seismic refraction line are used to calculate a 2.5-D gravity model. The P-wave velocity model shows an unusual ∼3-km-thin oceanic crust with seismic velocities less than 6.3 km s−1, indicating the absence of a significant oceanic layer 3. Mantle velocities vary between 7.5 kms−1 in the uppermost mantle and 8.0 km s−1 at approximately 15 km depth. The low velocities within the upper mantle may be explained by 13 per cent serpentinisation, which is negligible at about 15 km depth. Furthermore, the S-wave velocity model shows low Vp/Vs ratios in the mantle, indicating a highly serpentinised mantle at shallow depths. The gravity model has crustal densities between 2.3 and 2.9 g cm−3, which also point towards the absence of a significant thick oceanic layer 3. The results of our seismic refraction line and other geophysical data indicate that the entire Boreas Basin opened at ultraslow spreading rates since at least ∼28 Ma. No evidence for an extinct spreading ridge in the centre of the Boreas Basin was found.
    Repository-Name: EPIC Alfred Wegener Institut
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  • 16
    Publikationsdatum: 2022-05-26
    Beschreibung: © The Author(s), 2013. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Genome Biology and Evolution 5 (2013): 2368-2381, doi:10.1093/gbe/evt179.
    Beschreibung: The dinoflagellates are an evolutionarily and ecologically important group of microbial eukaryotes. Previous work suggests that horizontal gene transfer (HGT) is an important source of gene innovation in these organisms. However, dinoflagellate genomes are notoriously large and complex, making genomic investigation of this phenomenon impractical with currently available sequencing technology. Fortunately, de novo transcriptome sequencing and assembly provides an alternative approach for investigating HGT. We sequenced the transcriptome of the dinoflagellate Alexandrium tamarense Group IV to investigate how HGT has contributed to gene innovation in this group. Our comprehensive A. tamarense Group IV gene set was compared with those of 16 other eukaryotic genomes. Ancestral gene content reconstruction of ortholog groups shows that A. tamarense Group IV has the largest number of gene families gained (314–1,563 depending on inference method) relative to all other organisms in the analysis (0–782). Phylogenomic analysis indicates that genes horizontally acquired from bacteria are a significant proportion of this gene influx, as are genes transferred from other eukaryotes either through HGT or endosymbiosis. The dinoflagellates also display curious cases of gene loss associated with mitochondrial metabolism including the entire Complex I of oxidative phosphorylation. Some of these missing genes have been functionally replaced by bacterial and eukaryotic xenologs. The transcriptome of A. tamarense Group IV lends strong support to a growing body of evidence that dinoflagellate genomes are extraordinarily impacted by HGT.
    Beschreibung: J.H.W. was supported by the NSF IGERT Program in Comparative Genomics at the University of Arizona (grant number DGE-0654435). This work was supported by grants from the National Science Foundation (grant numbers OCE-0723498, EF-0732440) and funding provided by the BIO5 Institute at the University of Arizona to J.D.H.
    Schlagwort(e): Gene innovation ; Alexandrium tamarense Group IV ; Phylogenetic profile ; Phylogenomics ; De novo transcriptome assembly ; Mitochondrial metabolism
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  • 17
    facet.materialart.
    Unbekannt
    Oxford University Press
    Publikationsdatum: 2022-05-26
    Beschreibung: Author Posting. © Author, 2014. This article is posted here by permission of The Royal Astronomical Society for personal use, not for redistribution. The definitive version was published in Geophysical Journal International 198 (2014): 622-636, doi: 10.1093/gji/ggu121.
    Beschreibung: The robust statistical model of a Gaussian core contaminated by outlying data that underlies robust estimation of the magnetotelluric (MT) response function has been re-examined. The residuals from robust estimators are systematically long tailed compared to a distribution based on the Gaussian, and hence are inconsistent with the robust model. Instead, MT data are pervasively described by the alpha stable distribution family whose variance and sometimes mean are undefined. A maximum likelihood estimator (MLE) that exploits the stable nature of MT data is formulated, and its two-stage implementation in which stable parameters are first fit to the data and then the MT responses are solved for is described. The MLE is shown to be inherently robust, but differs from the conventional robust estimator because it is based on a model derived from the data, while robust estimators are ad hoc, being based on the robust model that is inconsistent with actual data. Propriety versus impropriety of the complex MT response was investigated, and a likelihood ratio test for propriety and its null distribution was established. The Cramér-Rao lower bounds for the covariance matrix of proper and improper MT responses were specified. The MLE was applied to exemplar long period and broad-band data sets from South Africa. Both are shown to be significantly stably distributed using the Kolmogorov–Smirnov goodness of fit and Ansari-Bradley non-parametric dispersion tests. Impropriety of the MT responses at both sites is pervasive, hence the improper Cramér-Rao bound was used to estimate the MLE covariance. The MLE is shown to be nearly unbiased and well described by a Gaussian distribution based on bootstrap simulation. The MLE was compared to a conventional robust estimator, establishing that the standard errors of the former are systematically smaller than for the latter and that the standardized differences between them exhibit excursions that are both too frequent and too large to be described by a Gaussian model. This is ascribed to pervasive bias of the robust estimator that is to some degree obscured by their systematically large confidence bounds. Finally, a series of topics for further investigation is proposed.
    Beschreibung: This work was supported by NSF grant EAR0809074.
    Schlagwort(e): Time series analysis ; Numerical approximations and analysis ; Fractals and multifractals ; Probability distributions ; Magnetotellurics
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  • 18
    Publikationsdatum: 2022-05-26
    Beschreibung: © The Author(s), 2014. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Journal of Plankton Research 36 (2014): 943-955, doi:10.1093/plankt/fbu029.
    Beschreibung: The mechanisms by which phytoplankton cope with stressors in the marine environment are neither fully characterized nor understood. As viruses are the most abundant entities in the global ocean and represent a strong top-down regulator of phytoplankton abundance and diversity, we sought to characterize the cellular response of two marine haptophytes to virus infection in order to gain more knowledge about the nature and diversity of microalgal responses to this chronic biotic stressor. We infected laboratory cultures of the haptophytes Haptolina ericina and Phaeocystis pouchetii with CeV-01B or PpV-01B dsDNA viruses, respectively, and assessed the extent to which host cellular responses resemble programmed cell death (PCD) through the activation of diagnostic molecular and biochemical markers. Pronounced DNA fragmentation and activation of cysteine aspartate-specific proteases (caspases) were only detected in virus-infected cultures of these phytoplankton. Inhibition of host caspase activity by addition of the pan-caspase inhibitor z-VAD-fmk did not impair virus production in either host–virus system, differentiating it from the Emiliania huxleyi-Coccolithovirus model of haptophyte–virus interactions. Nonetheless, our findings point to a general conservation of PCD-like activation during virus infection in ecologically diverse haptophytes, with the subtle heterogeneity of cell death biochemical responses possibly exerting differential regulation on phytoplankton abundance and diversity.
    Beschreibung: Funding to J.L.R, R.-A.S. and A.L. was provided by the Norwegian Research Council for the “VIPMAP” (nr. 186142) and “HAPTODIV” (nr. 190307) projects, and by the European Research Council Advanced Grant ERC-AG-LS8 “Microbial Network Organisation” (MINOS, project number 250254). J.L.R. received a FRIBIO overseas research fellowship from the Norwegian Research Council. K.D.B. and B.V.M. were supported by funding from the United States National Science Foundation (OCE-1061883).
    Schlagwort(e): Caspase ; DNA fragmentation ; IETD ; Phycodnaviridae ; z-VAD-fmk ; Haptophyte
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  • 19
    Publikationsdatum: 2022-05-26
    Beschreibung: © The Author(s), 2014. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Genome Biology and Evolution 6 (2014): 2210-2217, doi:10.1093/gbe/evu177.
    Beschreibung: The alpha subunits of voltage-gated calcium channels (Cavs) are large transmembrane proteins responsible for crucial physiological processes in excitable cells. They are assisted by three auxiliary subunits that can modulate their electrical behavior. Little is known about the evolution and roles of the various subunits of Cavs in nonbilaterian animals and in nonanimal lineages. For this reason, we mapped the phyletic distribution of the four channel subunits and reconstructed their phylogeny. Although alpha subunits have deep evolutionary roots as ancient as the split between plants and opistokonths, beta subunits appeared in the last common ancestor of animals and their close-relatives choanoflagellates, gamma subunits are a bilaterian novelty and alpha2/delta subunits appeared in the lineage of Placozoa, Cnidaria, and Bilateria. We note that gene losses were extremely common in the evolution of Cavs, with noticeable losses in multiple clades of subfamilies and also of whole Cav families. As in vertebrates, but not protostomes, Cav channel genes duplicated in Cnidaria. We characterized by in situ hybridization the tissue distribution of alpha subunits in the sea anemone Nematostella vectensis, a nonbilaterian animal possessing all three Cav subfamilies common to Bilateria. We find that some of the alpha subunit subtypes exhibit distinct spatiotemporal expression patterns. Further, all six sea anemone alpha subunit subtypes are conserved in stony corals, which separated from anemones 500 MA. This unexpected conservation together with the expression patterns strongly supports the notion that these subtypes carry unique functional roles.
    Schlagwort(e): Voltage-gated calcium channel ; Ion channel ; Cnidaria ; Nematostella vectensis ; Evolution of nervous system
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  • 20
    Publikationsdatum: 2022-05-26
    Beschreibung: © The Author(s), 2012. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Nucleic Acids Research 40 (2012): 7132-7149, doi:10.1093/nar/gks467.
    Beschreibung: The capacity of microorganisms to respond to variable external conditions requires a coordination of environment-sensing mechanisms and decision-making regulatory circuits. Here, we seek to understand the interplay between these two processes by combining high-throughput measurement of time-dependent mRNA profiles with a novel computational approach that searches for key genetic triggers of transcriptional changes. Our approach helped us understand the regulatory strategies of a respiratorily versatile bacterium with promising bioenergy and bioremediation applications, Shewanella oneidensis, in minimal and rich media. By comparing expression profiles across these two conditions, we unveiled components of the transcriptional program that depend mainly on the growth phase. Conversely, by integrating our time-dependent data with a previously available large compendium of static perturbation responses, we identified transcriptional changes that cannot be explained solely by internal network dynamics, but are rather triggered by specific genes acting as key mediators of an environment-dependent response. These transcriptional triggers include known and novel regulators that respond to carbon, nitrogen and oxygen limitation. Our analysis suggests a sequence of physiological responses, including a coupling between nitrogen depletion and glycogen storage, partially recapitulated through dynamic flux balance analysis, and experimentally confirmed by metabolite measurements. Our approach is broadly applicable to other systems.
    Beschreibung: Office of Science (BER), U.S. Department of Energy [DE-FG02-07ER64388 to D.S. and DE-FG02- 08ER64511 to M.H.S.]; National Aeronautics and Space Administration, NASA Astrobiology Institute [NNA08CN84A to D.S.].
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  • 21
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4455-4461 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Intermolecular potentials for Ar and Kr interacting with HBr are obtained by least-squares fitting of potential parameters to data obtained from the molecular-beam microwave spectra of the Ar–HBr and Kr–HBr van der Waals complexes. The equilibrium geometry is linear Rg–H–Br in each case, but there are substantial secondary minima at the linear Rg–Br–H geometries; for Ar–HBr, the secondary minimum is only about 5 cm−1 shallower than the primary minimum. This potential feature is found to explain the anomalous H/D isotope effects in centrifugal distortion constants that have been observed for the Rg–HBr complexes. It is predicted that Ar–HBr will have a very low-energy bending state, only 11 cm−1 above the ground state, arising from the secondary minimum.
    Materialart: Digitale Medien
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  • 22
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4477-4484 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Excited rotational level dependence of the external magnetic field effects both on intensity and on decay of fluorescence of pyrazine vapor has been carefully examined for the zero-point vibrational level in S1 with a field strength of 0–170 G. The magnetic quenching of the slow fluorescence becomes more effective with increasing rotational quantum number J' of the excited level, and the field strength at which the amount of fluorescence quenching becomes one-half of the total amount of quenching at the saturated fields is roughly proportional to (2J'+1)−1. The magnetic quenching is also found to depend on K' of the excited level. The rotational level dependence of the magnetic quenching of the slow fluorescence is related to a difference in the number of the triplet levels coupled to the optically excited singlet rovibronic level, based on the spin decoupling mechanism of the singlet–triplet mixed level.
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  • 23
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4499-4503 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: We have observed many collision-induced-dipole (CID) absorption bands arising from the transitions between quasimolecular ground and high-lying (n≤10) states in the strontium–rare-gas systems. For each absorption band, we have measured the energy shift of the absorption peak from the energy of the correlating atomic forbidden transition and the effective oscillator strength per unit perturber density fCID/Np. The shift is roughly proportional to the electron scattering length L0 for each rare-gas atom, whereas the fCID/Np is roughly proportional to L20. The shift decreases in general as the principal quantum number n increases, and increases as one goes from the s state to the d state, and to the degenerate manifold state with l≥3. These general features of the shift and fCID/Np are consistent with the predictions by a simple Fermi-potential model, suggesting the important role of the interaction between a Rydberg electron and a rare-gas atom in the CID absorption processes.
    Materialart: Digitale Medien
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  • 24
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4582-4586 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The ν2 band of the silylene SiH2 molecule in X˜ 1 A1 was observed for the first time in the gas phase by using infrared diode laser kinetic spectroscopy. Silylene molecules were generated by the photolysis of phenylsilane at 193 nm. The observed spectrum was analyzed to determine the rotational and centrifugal distortion constants in the ground and v2 =1 states and the band origin ν0 =998.6241(3) cm−1 with one standard deviation in parentheses. The significance of the derived parameters is discussed in detail.
    Materialart: Digitale Medien
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  • 25
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4597-4602 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Using translational spectroscopy we have studied the d 1Πg and C 3 Πg Rydberg states of O2 . The dissociation of the vibrational levels v=0–2 to all energetically accessible dissociation limits has been followed. The dissociation pathways directly reflect the predissociation mechanisms involved. For the d 1 Πg Rydberg state competition between predissociation by a 3 Πg valence state, due to singlet–triplet mixing, and by a 1 Πg valence state has been observed. Using the Fermi golden rule the observed vibrationally dependent competition is reproduced, corroborating the positions of the lower 1 Πg and 3 Πg valence state curves and yielding various coupling strengths.
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  • 26
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4636-4642 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Rotationally inelastic scattering of carbon dioxide by translationally hot H, D, and Cl atoms was studied by time-resolved diode laser absorption. The high J rotational distribution falls off quite rapidly between J=60 and J=80. D atom collisions have roughly twice the excitation cross section versus H atom collisions, with the H*/D* ratio decreasing with increasing J. These results are consistent with a constraint on the total reagent orbital angular momentum available for rotational excitation. Transient Doppler profiles measured immediately after hot atom/CO2 collisions indicate that CO2 molecules excited to high J levels have a larger recoil velocity than molecules excited to lower J levels. This result is consistent with predictions based on a simple model which treats the CO2 potential as a hard shell ellipsoid.
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  • 27
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4643-4650 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The molecular dynamics simulation method is extended to study a model of diffusion-controlled reactions. This allows a molecular description of solvent at an equal footing of reactants. Nondiffusional dynamic behavior of reactive molecules is found at short times. It enhances the rate of reactive encounter in comparison to the prediction of Smoluchowski theory. The model studied in this work can be regarded as a theoretical prototype of fluorescence quenching. In this context it is shown that the nondiffusional dynamics is mainly responsible for the discrepancy between Stern–Volmer plots measured in a continuous excitation experiment or obtained by integrating the time resolved fluorescence intensity. The other aspects such as the long-time behavior of survival probability, solvent effect as well as competing effect from finite concentration of one reactive species are also studied in some detail.
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  • 28
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4714-4727 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The reactions of neutral iron clusters Fe7–27 with water are studied in a laser-vaporization cluster source coupled to a continuous-flow reactor. Reaction products are detected via laser ionization and time-of-flight mass spectrometry. The reactions of room-temperature clusters with H2O show adsorbate decomposition and hydrogen desorption, as do the reactions with D2O at elevated temperatures. The room-temperature reaction with D2O appears not to involve any decomposition, and is at equilibrium under the conditions of these experiments. The dependence of reaction extent on D2O pressure yields equilibrium constants for the addition of the first and second D2O molecules. The analysis is complicated by the presence of two-photon ionization processes that are treated quantitatively with a rate-equation model. This treatment also yields estimates for cluster photoabsorption cross sections, which are found to be approximately linear in cluster size, having a magnitude of 2.3×10−17 cm2 per iron atom. From the derived equilibrium constants and estimated adsorption entropies, approximate D2O–cluster binding energies are determined. They range from 0.42 to 0.59 eV, and their dependence on cluster size shows a remarkable similarity to the dependence of the rate constants for reaction of iron clusters with H2. The implications of this similarity are discussed.
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  • 29
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4738-4744 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Relativistic effect Erel upon the total electronic energy of an atom is discussed with particular reference to obtaining the nonrelativistic total energy Eexact from the experimental total energy. Numerical values of this effect obtained by various authors by different nonempirical methods are compared for neutral atoms of rare-gas elements. It is shown that methods either of a Hartree–Fock-type or of a Dirac–Hartree–Fock-type give much the same Erel value for He through Ar. It is pointed out that Erel calculated with Hartree–Fock wave functions is not adequate for use in obtaining Eexact from the experimental total energy and that the Erel value calculated with wave functions including electron correlation should work well, although an actual demonstration can be done only for two-electron systems for lack of data. A semiempirical formula is therefore proposed, which is useful for least-squares fit of experimental total energies of isoelectronic series of atoms to extract nonrelativistic total energies along with the relativistic effect. From nonrelativistic energies thus derived, semiempirical values of correlation energies of atoms are obtained. The results thus obtained are in reasonable agreement with correlation energies derived by Clementi along somewhat different lines. The power series expansion in Z of the fitted formula for the He series shows that numerical values of expansion coefficients agree reasonably well with the corresponding values obtained by accurate relativistic and nonrelativistic Z expansion-type calculations.
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  • 30
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4785-4792 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The ground and low-lying states of CuF2 and CuCl2 have been studied using the single and doubles configuration interaction (SDCI) and coupled pair functional (CPF) methods in a large Gaussian basis set including up to g-type functions. The results include a determination of the bond distances for all the ligand field states (the three states with one hole in the 3d shell) and charge transfer (CT) states, and force constants for the ligand field states. Overall the SDCI (with or without the Davidson correction for higher excitations) and CPF results are in good agreement. The CPF results, which we believe to be the most accurate, can be summarized as follows. The computed value for the asymmetric stretching frequency in the 2Σ+g ground state of CuF2 is 740 cm−1, compared to the experimental value of 765 cm−1. The d–d transition energies for CuF2 are 2500 and 10 800 cm−1. The two lowest charge transfer states are at 31 200 and 33 900 cm−1, respectively. CuCl2 has been found to have a ground state which is an almost equal mixture of 2Σ+g and 2Πg when an estimate of the spin–orbit interaction is included. Three d–d transitions are found: 1600 cm−1 ( J=1/2), 7500 cm−1 (J=3/2), and 9700 cm−1 (J=5/2). The lowest charge transfer states have been computed to lie at 16 700 and 19 600 cm−1. Two bands have been found in the gas-phase spectrum of CuCl2 at 9000 and 19 000 cm−1, in good agreement with the present results. The computed f value for the CT band is 0.017, to be compared to the experimental value of 0.014.
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  • 31
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4909-4911 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The dissociation equilibrium AlBr=Al+Br was studied by effusion beam mass spectrometry over the range 1970 to 2260 K and the dissociation energy D00(AlBr) was derived as 4.41±0.06 eV. This value is in general agreement with other fragmentary thermochemical results, but it is lower than a value derived from a short extrapolation of vibrational levels in the excited 1π state, doubtless because of a potential maximum of about 0.22 eV in that state. A Birge–Sponer extrapolation of the ground state vibrational levels, when corrected for degree of ionicity, yields a D00 value in close accord with the experimental result, but an electrostatic model calculation falls short by 0.45 eV.
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  • 32
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4920-4925 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: A new scheme of experimental criterion is proposed for estimating the carrier mobility and main-chain conformation of an electroactive polymer chain by the technique of transient electric birefringence (TEB). The rise response Δnr (t) and the decay response Δnd (t) in the TEB satisfy in the Kerr regime (i) Δnr (t)=Δnst -Δnd (t) for a polymer molecule of arbitrary conformation with an induced dipole moment alone arising from carriers highly mobile along the main chain, (ii) Δnr (t)=Δnst -(3/2)Δnd (t/3)+(1/2)Δnd (t) for a rodlike polymer molecule with a permanent dipole moment alone originating from carriers with low mobility, and (iii) Δnr(t)=Δnst-2Δnd (t/2)+Δnd (t) for a random-coiled polymer with a permanent dipole moment alone due to low-mobility carriers, where Δnst =limt→∞ Δnr(t) . Then, comparison of the TEB rise and decay responses gives us information on the carrier mobility and main-chain conformation. This criterion is valid also for polydispersed polymer samples. By applying the criterion to the exemplifying data of the TEB responses for soluble urethane-substituted polydiacetylenes, it is found that the polydiacetylene molecules take a random-coil conformation with a permanent dipole moment in a good solvent, while in a poor solvent the carrier mobility depends crucially on the solvent condition.
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  • 33
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4942-4948 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The rate of catalytic carbon monoxide oxidation on a Pt(100) single crystal surface under isothermal, low-pressure conditions exhibits for certain ranges of parameters (O2 and CO partial pressures, temperature) sustained temporal oscillations whose mechanism had been explored in previous work. Coupling between reaction and diffusion leads to spatial pattern formation as manifested by patches with different work function on the intrinsically homogeneous surface. Imaging is performed by means of the novel technique of scanning photoemission microscopy. Typically, nuclei with dimensions of a few microns, as determined by the instrumental resolution, are formed spontaneously and expand with sharp fronts and velocities of about 0.5 mm/min (at 480 K) up to sizes ≥1 mm. Waves with even more extended fronts propagating with somewhat higher velocities across the sample surface are responsible for the occurrence of large amplitude temporal oscillations of the integral reaction rate.
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  • 34
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4338-4345 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Carbon K edge near edge x-ray absorption fine structure (NEXAFS) spectra of adsorbed acetonitrile and reactive intermediates derived therefrom on Ag(110) were studied in order to determine their orientation and bonding to the surface. For both the multilayer and the adsorbed monolayer there is excellent agreement between the spectra of the adsorbed acetonitrile and the gas phase species. For the multilayer coverage the orientation of the acetonitrile molecules is not completely random; the molecules prefer an orientation with their bond axes closer to parallel than perpendicular to the surface. At monolayer coverage acetonitrile bound to the surface is unrehybridized. It is bound with its linear molecular skeleton parallel to the surface and randomly oriented azimuthally. Annealing molecular CH3 CN to 325 K in the presence of coadsorbed atomic oxygen produces a linear CH2 CN surface intermediate, the molecular axis of which is parallel to the surface and perpendicular to the close-packed direction. The C–C and C–N bond lengths are essentially unperturbed from their values in gas phase CH3 CN. Bonding appears to occur between the methylene carbon and the metal, as expected. A broadening of the π* resonance for transition into the π* orbital perpendicular to the surface is interpreted in terms of π-donor bonding.
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  • 35
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4265-4272 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Attenuated total reflectance (ATR) from principal faces of orthorhombic (and higher symmetry) crystals in spectral regions including strongly polar optic modes is considered. A detailed, quantitative comparison between experimental and calculated ATR infrared (IR) spectra of orthorhombic sodium nitroprusside dihydrate (SNP), Na2[Fe(CN)5NO]⋅2H2O, single crystals in the 500–3800 cm−1 region is presented. Calculated ATR spectra are generated employing the dielectric tensor of SNP obtained from Kramers–Kronig analysis of external reflectance data. The dependence of intensities, profiles, and locations of bands in the spectra upon the relative refractive index of the sample against the ATR prism and the polarization state of the reflected IR beam will be discussed. Both theoretical and experimental evidence of the coupling of the TM-polarized evanescent wave with strong in-plane-polarized optic modes at about their LO frequencies will be given with reference to the case of the strong NO stretching mode of SNP. Finally, the computed and experimental ATR results in SNP single crystals will be critically compared with powder ATR data and reported polarized IR transmittance spectra of SNP single crystals plates.
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  • 36
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4299-4306 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: X-ray diffraction data for liquid n-butane near the triple and boiling points are presented. The data are analyzed using scattering factors for −CH3 and −CH2 groups which permits extraction of structure and distribution functions for carbon sites. An intramolecular carbon–carbon distance at approximately 3.1 A(ring) is assigned to a short end-to-end distance in a near-gauche conformation, which is in agreement with the electron diffraction results for gaseous n-butane. The intermolecular pair distribution functions show a large difference in the liquid structure for the low and high temperature states, similar to that found in liquid propane.
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  • 37
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4330-4337 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: We report studies of the kinetics of thermal desorption of In from Ga-stabilized GaAs(100) in ultrahigh vacuum. The relative coverage of In was monitored by x-ray photoelectron spectroscopy (XPS), while the substrate temperature was accurately measured using infrared laser interferometric thermometry. The In was deposited on GaAs by dosing, at room temperature, to saturated monolayer coverage with trimethylindium, yielding In ∼2×1014 cm−2. Subsequent heating to 400 °C desorbs all hydrocarbon species without affecting the In coverage. Further heating leads to first-order desorption of In, as confirmed by exponential decay of In(3d 5/2) XPS signal in isothermal desorption experiments at 473 and 503 °C. From temperature programmed desorption studies through the range 450 to 530 °C, differentiation of the In coverage vs time yielded desorption rates from which Arrhenius parameters were extracted. The unit-weighted average values of the preexponential factor and the desorption energy, obtained from three experiments with heating rates from 0.6 to 3.2 °C/min, are: log10A(s−1)=12.2±0.5 and Ed=53.5±1.2 kcal/mol, where the uncertainties are 1σ sample standard deviations. The Arrhenius parameters of desorption of In from Ga-stabilized GaAs(100) are found to be similar to those of vaporization of pure In. This is consistent with the known tendency of In to form islands on GaAs surfaces, but could also reflect the similarity of the local environments of an In atom adsorbed on an In island and an In atom adsorbed on a Ga-terminated surface. The observed first-order kinetics and the constancy of the In(3d 5/2) XPS signal up to the temperature where desorption occurs indicates that if islands are formed they are small (〈10 A(ring) diameter) at the low coverage used here.
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  • 38
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4360-4368 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Cooperative diffusion D of polyacrylamide gels in water was investigated by quasielastic light scattering both under the isotropically swollen state and under the uniaxially stretched and swollen state. The concentration (Ce) dependence of D for the isotropic gels having equilibrium degrees of swelling was measured by systematically changing crosslinking density of gels. The results yielded D=(3.4±0.5)×10−6 C0.76±0.03e cm2/s, in accord with a scaling prediction. For each of the gels prepared and having a given Ce, the uniaxial stretching was applied, and the values D were investigated as a function of extension ratio α and direction β with respect to the stretching direction. The results gave D (α,Ce)=(3.4±0.5)×10−6 αx Cye cm2/s, where x=2/3 for β=0° and −1/4 for β=90°, and y=0.76, independent of α and β. The results clearly indicate that upon increasing α, D increases and decreases, respectively, in the direction parallel and perpendicular to the stretching direction, implying suppression and enhancement of the concentration fluctuations as a result of the network being stiffened and softened in the respective directions.
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  • 39
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4387-4400 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The discrete chain representation of multiple scattering theory of the concentration dependence of the hydrodynamics of polymer solutions is applied to the calculation of the leading concentration correction to the dynamic structure factor S(k,t) and its first and second cumulants of individual labeled Gaussian chains in theta solutions at nonzero concentrations. Contributions are separated into those from overall translational and internal chain motions as well as couplings between different internal modes and between translation and internal modes, coupling that are introduced by interchain hydrodynamic interactions. The separate contributions are analyzed as a function of k and of t in order to isolate regions where certain contributions are dominant. As expected, short times and larger k tend to favor contributions from internal chain dynamics, while longer times and smaller k make concentration dependent translational effects predominate. Computations for shorter chains are extrapolated to provide the asymptotic long chain behavior.
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  • 40
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4418-4419 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The interconversion tunneling frequencies for (HCl)2 and (DCl)2 are obtained from near-infrared absorption spectra of the H(D)Cl stretching transitions, to spectroscopic precision for the mixed 35Cl–37Cl dimers. A phenomenological model of the interconversion process explains several experimental observations, and provides good estimates of the splittings expected for the 35Cl–35Cl and 37Cl–37Cl species.
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  • 41
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4425-4426 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The dissociation energy of boron hydride has been calculated ab initio using a very accurate theoretical model, with an expected accuracy of ±0.2 kcal mol−1. The values of 85.7 and 82.4 kcal mol−1 for De and D0, respectively, confirm the conclusion of Curtiss and Pople [J. Chem. Phys. 90, 2522 (1989)], that the predissociation limit of 82.6±0.4 kcal mol−1 might be close to the actual dissociation energy, and that an earlier proposed De of 78.9 kcal mol−1 is in error.
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  • 42
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3525-3531 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The ultrafast photodynamics of four-coordinate nickel(II) porphyrins in noncoordinating solvents has been studied using femtosecond time resolved optical spectroscopy. Unambiguous evidence has been found for the formation of a metastable metal (d,d) excited state in less than 350 fs following excitation of the macrocycle. However, the transient absorption spectrum of this ligand-field electronic excited state continues to evolve and reaches the steady-state form only after about 20 ps. This spectral behavior and the attendant complex kinetics can be modeled phenomenologically in terms of a broad distribution of the (d,d) excited states evolving to a narrower distribution. The dynamics are associated with vibrational relaxation. Intramolecular and intermolecular contributions to this process are considered.
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  • 43
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3571-3576 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: A new method for the calculation of bound state eigenvalues and eigenfunctions of the Schrödinger equation is presented. The Fourier grid Hamiltonian method is derived from the discrete Fourier transform algorithm. Its implementation and use is extremely simple, requiring the evaluation of the potential only at certain grid points and yielding directly the amplitude of the eigenfunctions at the same grid points.
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  • 44
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3631-3637 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The evaluation of free energy differences using the perturbation method or thermodynamic integration method requires special caution if multiple rotational isomeric states may exist in the system under investigation. In this article a recently suggested procedure to properly treat rotational isomeric states is illustrated with a molecular dynamics simulation of an aqueous solution of uncomplexed 18-crown-6 crown ether, as an example of a system in which large numbers of isomeric states may exist. By using very long molecular dynamics simulations, thermodynamic perturbation methods and symmetry arguments, the free energy of host organization into the conformation required to form the complex with K+ is estimated to be 2.6 kJ mol−1. It has also been found that the lowest energy conformations of 18-crown-6 in vacuo do not necessarily correspond to the most populated conformations in aqueous solution.
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  • 45
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3689-3699 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Pulsed neutron diffraction measurements have been made on liquid 1,2-dichloroethane-d4 (DCE). The wide momentum-transfer range (∼0.3–50 A(ring)−1) available has been used to further refine previously measured molecular structure parameters as well as to test the validity of the inelasticity corrections applied. A measurement using chlorine isotopes on a steady (reactor) source served to partially separate the chlorine–chlorine and the chlorine–carbon plus chlorine–deuterium correlations. The isotopic difference curves were then analyzed and the relevant features of the distribution of internal dihedral angles [P(τ)] obtained by adequate inversion of the experimental difference–functions. The intermolecular pair correlation function was then derived and both sets of functions (from pulsed and steady sources) are compared and tentatively assigned.
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  • 46
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3721-3723 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Brownian dynamics computer simulations are used to investigate the shape of the mean-squared end-to-end distance distribution function in the three regimes: (1) excluded volume; (2) θ; (3) collapsed. It is found that Mazur's function fits regime (1), that the Gaussian function fits regime (2), and that neither of these appear to describe the collapsed state. The implications of these results to theories of ring formation during polymerization is pointed out.
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  • 47
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5154-5159 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Using a purely ab initio minimum energy path for the trans-tunneling motion in the HF dimer, the energy levels for the K-type rotation and trans-tunneling motion for (HF)2 and (DF)2 are calculated with a one-dimensional semirigid bender Hamiltonian and no adjustable parameters. The transition moments for rotation-tunneling transitions are calculated, using our ab initio value for the dipole moment of an isolated HF molecule, and we also calculate B¯ values. The energy levels we obtain are in close agreement with experiment; for example, the K=0 tunneling splitting in (HF)2 is calculated as 0.65 cm−1 compared to the experimental value of 0.658 69 cm−1. As well as showing that our ab initio minimum energy path is very good, the calculation demonstrates that the semirigid bender formalism is able to account quantitatively for the unusual K dependence of the rotational energies resulting from the quasilinear behavior, and that the trans-tunneling motion is separable from the other degrees of freedom. We use the results to predict the locations, and transition moments, of the ΔK=0 and ±1 subbands in the tunneling spectra of (HF)2 and (DF)2, many of which have not yet been observed.
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  • 48
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5139-5153 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The problem of classical vs nonclassical structure of protonated acetylene (vinyl cation) C2H+3 has been studied using high resolution infrared spectroscopy. The spectrum has been observed in the 3.2 μm region in air-cooled and water-cooled plasmas using C2H2:H2:He mixtures and in liquid nitrogen-cooled plasmas using CH4:H2:He mixtures. The difference frequency spectrometer with the velocity modulation method has been used to conduct the Doppler-limited, high sensitivity spectroscopy.The observed vibration–rotation pattern with the band origin at 3142.2 cm−1 has been identified as due to the antisymmetric CH stretching ν6 band of the C2H+3 ion with the nonclassical (bridged) structure. The observed spectral pattern was anomalous, but definitive assignments could be made for a part of the spectrum using the ground state combination differences which fit to the usual asymmetric rotor pattern. The discrimination between the classical and nonclassical structures is based on the observed spectral intensity pattern due to spin statistical weights. Agreement of vibrational band patterns and the rotational constants with ab initio values gives supporting evidence. The anomaly of the spectrum is at least partly ascribed to the small energy difference between the classical and nonclassical structures and possible rearrangement between them, the idea used by organic chemists over the years in wet chemistry. Systematic splittings with the intensity ratio of 2:1 have been noticed in some parts of the spectrum indicating that the protons tunnel between the apex and the two end equilibrium positions of the bridged structure. Using a simplified internal rotation model proposed by Hougen, the barrier height of the tunneling has been estimated. Chemical kinetics in plasmas related to C2H+3 is also discussed.We conclude that (1) the nonclassical structure is lower in energy than the classical structure, and (2) the apex proton and the two end protons exchange their positions with a measurable time scale.
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  • 49
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5164-5169 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The inelastic neutron scattering (INS) spectra of some ammonium halides and ammonium nitrate are analyzed in terms of the internal vibrations of the NH+4 ion convoluted with multiphonon lattice modes up to the eighth term. Due to the low mass of this ion, most of the intensity of the internal-mode region of the INS spectra is in the "phonon wings,'' differences between the salts in this spectral region being mainly due to differences in their lattice-mode spectra. Refinement of the lattice Debye–Waller factor is included in the profile refinement of interatomic force constants.
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  • 50
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5160-5163 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: A new upper bound for the dissociation energy of acetylene, D00(HCC–H) =529.89(±0.01) kJ/mol, has been determined by Stark anticrossing spectroscopy. The zero-pressure extrapolated (unimolecular) decay rates of levels of S1 (A˜ 1Au) v'3=2 and 3 (quanta of the trans-bending vibration) increase upon application of an electric field of 113 kV/cm. We attribute this increase in molecular decay rate to predissociation rather than any other Stark-induced nonradiative or radiative phenomenon. The lowest level (v'3 =2, J'=2, K'=1) from which we have observed an increase in decay rate (i.e., predissociation) has an internal energy of 44 295.65 cm−1 relative to v=0, J=0 of S0 (X˜ 1∑+g). This corresponds to a value about 24 kJ/mol lower then the consensus upper bound result from four different recent experimental determinations (including one of ours) as well as current ab initio results. The new value agrees, however, with earlier work and with recent modeling studies of acetylene pyrolysis kinetics.
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  • 51
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3792-3793 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 52
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 2776-2778 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Electron paramagnetic resonance (EPR) studies performed at room tempertaure in Mn2+ doped Cs2NaYCl6 single crystals (elpasolite) showed that the Mn2+ ion occupies a tetragonal symmetry site in the cubic crystalline lattice. In contrast with previous results on elpasolite, where trivalent rare earth impurities occupy Oh sites, and divalent europium impurities occupy trigonal sites, this work reports, the first evidence of an impurity in a tetragonal symmetry site in this host with principal axes along 〈100〉 crystallographic directions. The unusually large total splitting of the EPR spectrum (∼10 000×10−4 cm−1) is discussed in order to establish a tentative model for the site.
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  • 53
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3596-3602 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Novel rigorous upper and lower bounds, at primitive level, to general electron-repulsion integrals (ERIs) involving Gaussian basis sets have been derived and interconnections with the earlier works in the literature are brought out. New optimal strategies for a preemptive elimination of insignificant ERIs at atom and contraction levels are discussed and tested, resulting in a significant reduction in CPU time. Similar analysis is carried out for the computation of the molecular electrostatic potential for the first time in the literature, leading to a marked savings in computer time.
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  • 54
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5185-5200 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Multiphoton ionization spectra have been obtained and analyzed for excitation in the 215–360 nm region from the X 3Σ−g, a 1Δg, and b 1Σ+g states of O2. The 0–0 band of the C 1Πg state is reported for the first time. Measurements of other vibrational bands terminating in the C 3Πg and d 1Πg states are in good agreement with determinations by other groups. Several vibrational levels (v'=0–5) of the 3dπg Rydberg complex have been assigned on the basis of (1) an analysis of the spin–orbit couplings between the (Λ,S) basis-set states, (2) spectral simulation, and (3) the behavior of the states when the excitation radiation is changed from linear to circular polarization.
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  • 55
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5201-5207 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Diode laser transient absorption/gain spectroscopy is used to monitor time-dependent populations of high rotational levels in OD (v=0) produced in the reaction of O(1D)+D2. Pure rotational transitions on species with large dipole moments offer good sensitivity, full state resolution and μs time resolution in the present apparatus. Measured nascent populations of OD in the four highest rotational levels thermodynamically accessible in this reaction are in reasonable agreement with the reported results of earlier laser-induced-fluorescence measurements, in which corrections for transition moments and predissociation introduce increasing uncertainties at high rotational levels. The relaxation kinetics of the highest rotational levels are not hopelessly complex, and evidence is presented for strong, but not complete propensity for conservation of Λ doublet symmetry during rotational relaxation.
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  • 56
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3647-3661 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: A consistent simulation of ionic or strongly polar solutes in polar solvents presents a major challenge from both fundamental and practical aspects. The frequently used method of periodic boundary conditions (PBC) does not correctly take into account the symmetry of the solute field. Instead of using PBC, it is natural to model this type of system as a sphere (with the solute at the origin), but the boundary conditions to be used in such a model are not obvious. Early calculations performed with our surface constrained soft sphere dipoles (SCSSD) model indicated that the dipoles near the surface of the sphere will show unusual orientational preferences (they will overpolarize) unless a corrective force is included in the model, and thus we implemented polarization constraints in this spherical model of polar solutions. More recent approaches that treated the surface with stochastic dynamics, but did not take into account the surface polarization effects, were also found to exhibit these nonphysical orientational preferences. The present work develops a surface constrained all-atom solvent (SCAAS) model in order to consistently treat the surface polarization effects in all-atom molecular dynamics simulations. The SCAAS model, which was presented in a preliminary way in previous works, introduces surface constraints as boundary conditions in order to make the necessarily finite system behave as if it was part of an infinite system. The performance of the model with regard to various properties of bulk water is examined by comparing its results to those obtained by PBC simulations. The results obtained from SCAAS models of different sizes are found to be similar to each other and to the corresponding PBC results. The performance of the model in simulations of solvated ions is emphasized and a comparison of the results obtained with spheres of different sizes demonstrates that the model does not possess significant size dependence. This indicates that the model can be used with a relatively small number of solvent molecules for convergent simulation of structure, energetics, and dynamics of polar solutions. The much simpler fixedcenter Langevin dipoles (FCLD) model is also examined and found to provide a powerful tool for estimating solvation free energies. Finally, a preliminary study of the dielectric properties of the SCAAS model is reported and the potential of this model for exploring the correct implementation of the solvent reaction field is discussed.
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  • 57
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3700-3706 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The first-order phase transition of the ferromagnetic Ising model driven by the magnetic field at temperatures below criticality is studied by Monte Carlo methods for a two-dimensional thin film geometry, L×M with two free boundaries of length M(very-much-greater-than)L, at which boundary fields act. This model study is relevant, in particular, for phase transitions in monolayers adsorbed at stepped surfaces. While in the bulk geometry (L→∞) this transition occurs for zero field in the present model, with the system "jumping'' from a state with uniformly positive magnetization to a state with uniformly negative magnetization, in the thin film geometry the transition occurs at a critical field H*∼L−1, and the two states between which the transition occurs are characterized by strongly nonuniform magnetization profiles across the film. These findings are in agreement with the scaling theory of Fisher and Nakanishi.
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  • 58
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3724-3728 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: A simplified stability condition for the Hartree–Fock (HF) solution giving the self-consistent field crystal orbitals (SCF-CO) of the infinite one-dimensional system is derived. Since the present formulation, particularly for the systems having nearly or entirely degenerated highest occupied and the lowest unoccupied COs, contains only two physical parameters, that is, the density of states and the Coulomb repulsion integrals both at the Fermi level, it is tractable to examine the stability of the HF solutions of such polymers as well as the ordinary molecular systems. An example of its application to metallic trans-type polyacetylene is also shown.
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  • 59
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3744-3761 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: An ensemble of distributed donor molecules that undergoes rotational transitions into a discrete excimer state has been analyzed, in an attempt to model distributed electronic relaxation and nonexponential fluorescence of aromatic polymers in presence of rotational sampling processes. In case of irreversible trapping, the donor survival function has been formulated in terms of the one-sided Laplace transform and specified for a modified Gaussian distribution to yield a closed-form expression for the donor decay. The formalism permits a time-dependent rate function to be derived that makes possible the construction of the excimer excitation function by means of the convolution theorem. In case of reversible constraints, a generalized treatment based upon time-dependent transition and transform matrices has been given which applies a perturbation technique for approximately solving the system of nonautonomous differential equations in the time domain. In the limit of weak coupling, the method develops approximate Mth order expressions (M=2,4,6, and 8) to the fluorescence response functions of donor and excimer. The perturbational solutions are well behaved up to relatively long time scales and they prove useful for providing the typical nonexponential time behavior of such a system affected by dispersion and dissociation. The physical restriction of this mathematical analysis (weak reversibility) has been addressed and the implications of distributed event times in future analyses of polymer fluorescence have been discussed.
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  • 60
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 2771-2775 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: 5,6-Dihydro-2H-thiopyran, CH2CH2CH=CHCH2S, has been synthesized and its far-infrared and Raman spectra recorded. Two series of sharp bands were observed originating from 139 and 235 cm−1 in the infrared spectrum for the out-of-plane ring-bending and the ring-twisting vibrations, respectively. A detailed energy level diagram including numerous excited states was determined for the two coupled vibrations. The two-dimensional potential energy surface, which satisfactorily fits more than two dozen observed transitions, was calculated to be V=2.431×104 x41 −0.383×104x21 +2.258×104x42 −1.966×104 x22 +1.026×105x21 x22 , where x1 is the ring-bending coordinate and x2 is the ring-twisting coordinate. The minimum energy on the potential surface corresponds to a twisting angle of 37.8° (the half-chair conformation). The lowest energy bent (boat) conformation corresponds to a saddle point 4130 cm−1 above the twisted conformation on the potential energy surface. The results are compared to analogous molecules and to molecular mechanics calculations.
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  • 61
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 2808-2813 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Photoabsorption cross sections of thiirane and thietane vapors have been studied in the 110–240 nm region using synchrotron radiation. A number of peaks from thiirane and thietane are arranged into four and five Rydberg series, respectively, converging to the first ionization potential. Many Rydberg peaks from both molecules are observed to possess vibronic structures. The vibrational progressions from thiirane are assigned to the CH2 wagging (ν4) and CS symmetry stretching (ν5) modes. For thietane, the CH2 wagging (ν5) and CS symmetry stretching (ν7) modes of the excited states are found to be active. Molecular geometries and vibrational frequencies for the excited states are discussed on the basis of ab initio calculations.
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  • 62
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 2840-2847 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Exact close-coupling calculations are used to evaluate the effectiveness of the coupled states approximation in the interpretation of low energy, noble gas methane collisions. The effect of the higher order angle dependent terms of the potential on the inelastic rotational transition was investigated. Calculations using only open channel basis functions were clearly different from converged calculations, but the differences were small enough to be negligible in comparison with experiment. It was shown that open channel coupled states calculations are of sufficient accuracy to evaluate the agreement of the potential model with experiment. The use of the coupled states approximation does not fully account for discrepancies between theory and experiment observed earlier.
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  • 63
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 2892-2897 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: A modified general model for radiationless energy transfer is examined. The model does not rely on selection criteria and is intended to apply over the range of diffusion and resonance energy transfer parameters normally encountered in quenching experiments. Experimental data is compared with theoretical predictions and found to confirm the model's validity for a wide range of physical conditions.
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  • 64
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 2912-2921 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The photodissociation of aluminum clusters, Al+n (n=7–17), has been studied over a broad energy range (1.88–6.99 eV). Measurements of the lifetimes of the photoexcited clusters are described. Dissociation energies have been determined by comparing the measured lifetimes with the predictions of a simple RRKM model. The dissociation energies show an overall increase with cluster size, but there are substantial oscillations around n=7–8 and n=13–15. Cluster cohesive energies are derived from these results and from previous measurements of the dissociation energies of the smaller clusters. The cohesive energies of the larger clusters (n〉6) are in good agreement with the predictions of a simple model based on the bulk cohesive energy and the cluster surface energy. However, the cohesive energies are substantially larger than the results of recent ab initio calculations. The photodissociation spectrum of Al+8 has been measured and shows a broad absorption feature with a maximum ∼470 nm.
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  • 65
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 2102-2107 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The microwave spectrum of dichlorosilylene SiCl2 has been observed to characterize this molecule of chemical interest. The molecule was generated by the thermal reaction between silicon powder and tetrachlorosilane at about 1000 °C. The rotational constants and the centrifugal distortion constants were determined for the three isotopic species Si35Cl2, Si35Cl37Cl, and Si37Cl2. The nuclear quadrupole coupling constants were determined from triplet hyperfine splittings observed for several transitions. The asymmetry of the Cl nuclear quadrupole coupling tensor was found to be very large and was accounted for by π electron backdonation from Cl to Si.
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  • 66
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 2971-2979 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The structures and stabilities of N2 and its 15 possible first-row isoelectronic analogs (CO, BF, BeNe, NO+, CF+, BNe+, O2+2, NF2+, CNe2+, OF3+, NNe3+, ONe4+, F4+2, FNe5+, and Ne6+2) have been examined using ab initio molecular orbital theory. Equilibrium structures have been obtained at a variety of levels of theory including MP3/6-311G(d) and ST4CCD/6-311+G(2df ) and dissociation energies determined at the MP4/6-311+G(3d2f ) level. Full potential energy curves for dissociation, including dissociation barriers, have been obtained at the CASSCF/6-311G(d) level. Spectroscopic constants have also been determined at this level. For the neutral and monocation analogs of N2, the calculated equilibrium geometries, dissociation energies, and spectroscopic constants are in good agreement with the experimental values. The dication analogs of N2, namely O2+2, NF2+, and CNe2+, are all found to be kinetically stable species lying in deep potential wells. In particular, the hitherto unobserved NF2+ dication is predicted to have a short equilibrium bond length (1.102 A(ring)) and a large barrier (445 kJ mol−1) to dissociation to N++F+. Thus NF2+ should be experimentally accessible in the gas phase. The (experimentally known) O2+2 dication is predicted to contain the shortest bond between any two heavy atoms, our best estimate of the bond length being 1.052 A(ring). The first excited state (A 3Σ+u) of O2+2 is predicted to be unbound, and observed metastable decomposition processes are reinterpreted in terms of the ground-state (X 1Σ+g) potential surface. In agreement with previous theoretical studies, we find that CNe2+ is a kinetically stable species, albeit with a relatively long C–Ne bond length. The OF3+ trication is calculated to have a relatively short bond but lies in a well of depth only 23 kJ mol−1. The potential energy curves of the other highly charged species are found to be purely repulsive.
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  • 67
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3002-3011 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The relative efficacy of using low order trucations with large reference space vs high order methods with small reference space is tested by comparing quasidegenerate many-body perturbation theory (QDMBPT) calculations of potential curves for the five lowest electronic states of LiH with the multireference coupled cluster calculations of Ben-Shlomo and Kaldor [J. Chem. Phys. 89, 956 (1988)]. The infinite order coupled cluster calculations use two configurational reference spaces involving the 2σ, 3σ, and 1π orbitals, while the QDMBPT computations are truncated at either second or third orders and employ the full active reference space formed either from the 2σ, 3σ, and 1π or from the 2σ, 3σ, 4σ, and 1π orbitals. This gives us the opportunity of testing the dependence of QDMBPT computations on the size of reference space, the available freedom in choosing valence orbitals and orbital energies, and the order of truncation. Second order, four valence orbital space QDMBPT calculations provide good agreement with the repulsive portion of the coupled cluster potentials, but yield a separated atom limit that is too high and that therefore distorts the remainder of the potential. Third order improves the separated atom limit considerably, providing good agreement with the coupled cluster calculations. The "full chemical'' five orbital reference space, on the other hand, yields very good agreement with coupled cluster potentials when using only the simpler second order QDMBPT calculations, and third order corrections in this case are very small but generally improve agreement with coupled cluster potentials. The five orbital reference space calculations are quite insensitive to a wide range of different choices of valence orbitals and orbital energies, demonstrating a robustness to the QDMBPT formalism used.
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  • 68
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3045-3055 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The hypernetted-chain (HNC) approximation is solved for fluids of dipolar hard ellipsoids and the structural, thermodynamic, and dielectric properties of the isotropic phase are discussed in some detail. Both prolate and oblate particles are considered and the isotropic–nematic transition is investigated using density functional theory (DFT). For fluids of prolate particles dipolar forces are found to have a significant effect upon the isotropic–nematic transition which occurs at lower densities as the dipole moment is increased. For the oblate case the dipolar interactions have only a very small, if any, influence upon the isotropic–nematic transition density. For both prolate and oblate particles the present HNC/DFT calculations do not predict ferroelectric nematic phases.
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  • 69
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5313-5315 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The ν3 (O–Si stretch) fundamental bands of the HOSi+ and DOSi+ molecular ions in the 9 μm region have been detected for the first time, using a tunable infrared diode laser spectrometer and a hollow cathode discharge cell. Analysis of the results yielded accurate values for the molecular rotational and centrifugal distortion parameters, as well as for the band origins, which are 1127.009 cm−1 for HOSi+ and 1103.112 cm−1 for DOSi+ . The ground vibrational state parameters are in excellent agreement with those determined from the ν1 bands of the two isotopes.
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  • 70
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5324-5328 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Fragment ions from N2 in the states of (K)−1(nl)1 have been measured at 54.7° with respect to the polarization direction of the incident photon by using a time-of-flight (TOF) mass spectrometer. Simulation fitting calculation to the measured TOF spectra gave distributions of the kinetic energy for these ions. Ion yield spectra observed showed that no singly charged molecular ion was produced from the states of (K)−1(nl)1 in contrast to that of (K)−1(1πg)1. These results are discussed in connection to the dissociation pathway of N2 in these states.
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  • 71
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5329-5334 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Dissociation of O2 stimulated by soft x-ray absorption has been studied by using a monochromatized synchrotron radiation and a time-of-flight mass spectrometer. The parent molecular ion O+2 was formed only at 531 eV (excitation of 1s→1πg), and a fragment ion O+ had the highest intensity in all the energies giving core–hole states. The measured time-of-flight spectra were reproduced by a simulation calculation, which provided kinetic energy distributions of O+ and O++. The dissociation pathways from the core–hole states of O2 were discussed using the obtained kinetic energy distribution and ion intensity ratios as well as Auger electron spectra in the literature.
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  • 72
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5316-5323 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The general theory for inelastic scattering of molecules 1Δ electronic states is outlined and applied to the specific case of 1Δ states arising from a π2 electron occupancy, e.g., NH(a 1Δ). Integral cross sections for rotational transitions out of the lowest rotational level (J=2) of NH(a 1Δ) v=0 are reported for several targets. A pulsed beam of rotationally cold NH(a 1Δ) was produced by 193 nm photolysis of a dilute mixture of hydrazoic acid in nitrogen seed gas at the tip of a nozzle. The target beam was also prepared as a pulsed supersonic beam. The final rotational state distribution was measured in the collision zone by laser fluorescence excitation. The state-to-state cross sections were found to decrease significantly with increasing final rotational quantum number J'. The magnitude of the J=2→J'=3 cross sections were compared for the different targets. Isotopic scrambling in NH(a 1Δ)–D2 collisions was also searched for but not observed.
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  • 73
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5335-5342 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The yield of metastable oxygen atoms through dissociative recombination of O+2 ions with electrons has been studied using a plasma flow tube experiment. For O+2 with high vibrational excitation (around v=9) it was found that half of the oxygen atoms are formed on the O(1D) state and that the branching ratio toward O(1S) is large (∼0.4). Using Xe+ instead of Ar+ as precursor ions, it was shown that the O(1S) yield is much less for ions with low vibrational excitation. However, the present experimental results are not compatible with the extremely low theoretical value of this yield which was reported recently for O+2 (v=0).
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  • 74
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5343-5351 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Quenching and vibrational energy transfer in the B2Π state of the NS free radical have been studied using temporally and spectrally resolved laser-induced fluorescence in a low-pressure discharge flow reactor. The collision partners were He, Ar, H2, N2, O2, SF6, CO2, and N2O. Total removal cross sections show an oscillatory behavior with v' in the range of unperturbed levels, v'=4–7, for all colliders studied save O2 where a nearly monotonic increase is seen. Vibrational transfer occurs for H2 and the polyatomics; the rates vary little with v'. Δv=2 transfer occurs with the polyatomic colliders for v'=5. Fluorescence decay traces from the perturbed v'=3 and 8 levels differ from the unperturbed levels and from each other. v'=3 is perturbed by quartets and shows "gateway'' level behavior whereas v'=8 is perturbed by a doublet and shows efficient interelectronic transfer for all rotational levels.
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  • 75
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5359-5364 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: State-to-state charge–transfer cross sections have been computed for N+2(X;v=0,1,2) +Ar at 12 collision energies between 1.2 and 320 eV. A classical path method is used, whereby the vibronic degrees of freedom are treated quantum mechanically as the system moves along a classical trajectory. The calculations use the potential energy surfaces computed by Archirel and Levy. Comparison is made with experimental results for this system, including the recent work from Ng's laboratory. In most cases the agreement is quite good. There is, however, a significant difference in the charge–transfer branching ratios to produce Ar+(2P3/2) or Ar+(2P1/2) products. Possible explanations of the discrepancy are discussed. As expected, the cross sections obey the Franck–Condon principle at energies above 200 eV.
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  • 76
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5352-5358 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Second virial coefficients as function of temperature are computed for the title molecular systems interacting with He, Ne, and Ar. The relevant anisotropic forces are obtained via accurate potential functions tested earlier through the analysis of several, different properties of the various systems. The relevant quantum corrections are also computed, in addition to the classical results, and their effects analyzed vis à vis the available experimental data. The influence of such corrections on the very low-T behavior of the virial coefficients and on the determination of the Boyle temperatures is also shown and discussed. All examined potential functions are found to yield B(T) values in rather good accord with experiments, in spite of their marked differences in anisotropic behavior and in the shape of their potential well regions.
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  • 77
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5365-5373 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The reaction between ground state atomic oxygen and acetylene was studied using the crossed molecular beam method with an average collision energy of 6 kcal/mol. The two major primary reaction channels are (a) formation of CH2 and CO and (b) formation of HCCO and H. Product angular distributions and time-of-flight spectra were measured and the translational energy release was determined for each channel. The reaction proceeds primarily on the triplet surface through a long-lived intermediate. For both channels the translational energy distributions were found to peak at about 30% of the total available energy, indicating the existence of an exit channel barrier in each case. The branching ratio between channel (a) and (b) was found to be 1.4±0.5.
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  • 78
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5387-5391 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: A pump-and-probe technique is utilized to yield a population distribution over the rotational quantum states of the nascent product MgH in the reaction of Mg(1P1) and H2. The resulting normalized profile of the MgH bimodal distribution at 693 K coincides with that at 733 K, as well as with the results obtained at 380 K by Breckenridge and co-workers. This temperature dependence demonstrates that the bimodality actually results from the insertive reaction alone. This conclusion is consistent with the isotopic effect.
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  • 79
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5374-5386 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Oscillations with large amplitudes (〉500 K), high frequencies (〉8 Hz), and good reproducibility are observed in methylamine decomposition on electrically heated Pt, Rh, and Ir wires at pressures of 0.25–8.0 Torr and temperatures between 900 and 1500 K. The major reaction involves formation of HCN which is endothermic by 37 kcal/mol, so that the reaction strongly cools the wire, which counteracts resistive heating. A photodiode array was used to monitor spatial and temporal oscillations with resolutions of 1 mm and 30 Hz, respectively. On Pt, the frequency increased with increasing pressure and with decreasing wire diameter, while amplitude was a weak function of these parameters. On Ir, oscillations were more complex with regions of the wire often oscillating independently and more variability between experiments. However, the overall behavior resembles that on Pt. On Rh, frequencies were much lower (〈0.03 Hz), oscillations occurred over a smaller temperature range and halves of the wire frequently oscillated out of phase with each other. Oscillatory behavior of methylamine decomposition on Pt was modeled by a simple lumped model which gives semiquantitative agreement with observations. The model assumes a simple unimolecular reaction with CH3NH2 adsorption blocked at low temperatures by formation of a strongly adsorbed CN which is known to be very stable on Pt (Ed (approximately-equal-to)50 kcal/mol). Calculated frequencies, pressure dependencies, amplitudes, and temperature range of oscillations agree quite well with experiments using reasonable values for adsorption and reaction rate parameters, and wire geometry and properties.
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  • 80
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5402-5411 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: A method to deconvolute experimental differential cross sections is presented. The procedure removes the effect of the angular divergence of the primary beam, the finite size of the detector, and multiple scattering. The resulting cross section is the optimal experimental result. The method also determines ε=nlQ0, the average number of times each beam particle is scattered. Here n is the number density of scattering gas, l is the length of the scattering region, and Q0 is the true absolute cross section. If the product nl is known, Q0 can be determined. Since the effect of the finite angular resolution of the apparatus has been removed, this method should yield accurate total cross sections. This, in turn, allows the differential cross section to be put on an absolute scale.
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  • 81
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5392-5401 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Quenching of highly excited vibrational states of NO2 in baths of CO2, N2O, and CO has been investigated. Dilute NO2 mixtures were excited by a pulse from an excimer pumped dye laser operating at 495 nm. The ν3 antisymmetric stretching modes of CO2 (2349 cm−1) and N2O (2223 cm−1) and the v=1 level of CO (2143 cm−1) were probed with continuous wave IR diode lasers. The amount of energy transferred from excited NO2 to the ν3 modes of both CO2 and N2O was found to be 3%±1% of the original excitation energy. On the other hand, a smaller amount of energy (0.9%±0.3%) was deposited into the CO vibrational mode for NO2 contained in a dilute CO bath. These results support a picture of very inefficient transfer from high energy states of donor molecules to the high-frequency vibrational modes of small bath molecules. Differences in the efficiency of energy reception by the high-frequency modes of these three molecules scale roughly as the infrared transition moments for the bath states indicating the importance of resonance effects in the energy transfer process, but a combination of short- and long-range force mechanisms is probably necessary to account for the observed differences.
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  • 82
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5412-5424 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The rate constant of a bimolecular gas-phase chemical reaction is determined by the energy distribution of the reactants and the cross section for the reaction. Systems in which photolysis and other nonequilibrium processes occur may have energy distributions which differ significantly from the equilibrium distribution. Analytical solutions are derived for the rate constant as a function of temperature for certain systems in which nonequilibium processes occur. The analytical solutions are compared with the numerical solutions and the agreement is found to be excellent, confirming the validity of the approximations that were made. Chemical reactions are simulated with the Monte Carlo method and the results again confirm the validity of the analytical solutions. Under certain nonequilibrium conditions, it is shown that the complex expression for the rate constant as a function of temperature reduces to a simple form, which resembles the Arrhenius equation. In this special case, the dependence of the results on the shape of the reaction cross section is investigated.
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  • 83
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5440-5443 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: In a recent paper it was shown that rare gas ions form bound molecular states which decay by emission of radiation in the VUV. They are potential candidates as storage media for VUV lasers. In the present investigation the ions Kr+K, Kr+Cs, Xe+K, and Xe+Cs are produced by electron beam excitation of suitable gas mixtures with He as buffer gas. Studies of the reaction kinetics were performed for Kr+K. The rate constant for the reaction Kr++K+He was determined to be 2.8×10−30 cm3 s−1. Kr+K is strongly quenched by plasma electrons and by reaction with Kr. The fluorescence yield at intense excitation was determined to be about 5×10−2 VUV quanta per He+ ion.
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  • 84
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 2124-2139 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Raman scattering in liquid (and in some cases in solid) isotopic mixtures of HC1 and DC1 is analyzed to prove recent theories by Bratos and Tarjus [Phys. Rev. A 32, 2431 (1985)], Logan [Mol. Phys. 58, 97 (1986)], and Knapp [J. Chem. Phys. 81, 643 (1984)] on vibrational line broadening in liquids. The concentration and temperature dependencies of isotropic [Ji(ω)] and anisotropic [Ja(ω)] line shapes have been studied between triple point (Tt) and critical temperature (Tc). It has been found that in accordance with the Bratos–Tarjus theory, Ji (ω) is much more sensitive of isotopic composition of the liquid than Ja(ω). An analysis of the concentration dependence of the broadening parameters near Tt illustrates the importance of cross correlations between the environmental broadening and the resonant intermolecular coupling. The spectral activity of three-particle resonant transfer also becomes significant. From the change of the maximum of Ji(ω) with isotopic dilution, which is a linear function of mole fraction, the dipole moment derivative δμ/δq is estimated to be more than twice that of its gas phase value. The asymmetry of the isotropic bands of both HC1 and DC1 changes with concentration at constant temperature. With increasing temperature, Ji(ω) of pure and diluted samples narrows as T−0.5 and T−0.3, respectively. Ji(ω) has been found to be intermediate between the slow and the fast modulation limit. From the high frequency wing of Ji (ω) the time constant of the zeroth order memory function was obtained. Its activation energy increases with increasing T. This is in qualitative agreement with the temperature dependence of the Enskog collision time and the spin–rotational correlation time. Taking into account the results of the Bratos–Tarjus theory, orientational correlation times τ(2) are determined from Ja (ω). The Raman method yields τ(2) values which are twice as long as those determined from NMR relaxation.
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  • 85
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1734-1753 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Theoretical investigations of the outer valence doubly ionized states of ethylene are presented using ab initio Green's function and configuration interaction methods. The vertical double ionization potentials computed by the Green's function method using the ADC(2) scheme are discussed in connection with the Auger spectrum of ethylene and found to reproduce the experimental spectrum quite accurately. Another main purpose of the present work is the investigation of the potential energy surfaces of selected states via ADC(2) and the study of the nuclear dynamics on them. It is shown that only the ground state of the dication is nonplanar with a torsional angle of 90°. The investigation of the topology of the surfaces reveals a low energy conical intersection of the dicationic ground and first excited states. The associated vibronic coupling problem turns out to include, additionally, the second excited state and thus, we encounter here a three-state problem. In the approximation of linear vibrational and vibronic coupling the static and dynamic aspects of the vibronic interaction are investigated by a model Hamiltonian comprising three nonseparable nondegenerate vibrational modes. The input data for the model are extracted from the ADC(2) results. With the aid of this Hamiltonian we have computed a hypothetical "sudden'' double ionization spectrum of ethylene whose complex structure is analyzed stepwise and by cuts through the pertinent adiabatic and diabatic surfaces. The analysis exhibits that the conical intersection of the two lower lying states dominates the vibronic dynamics and leads to strong vibronic mixing between them. This mixing is indirectly reinforced by the interaction between the intermediate and the upper states. As a consequence, strong nonadiabatic effects occur in the ethylene dication. Furthermore, two of the three surfaces involved in the conical intersection are also involved in a multidimensional avoided crossing. A more detailed analysis presented earlier has exhibited that the states belong to an interesting class where two potential energy surfaces are likely not to coincide although plenty of nuclear degrees of freedom exist, in principle, to allow for an intersection to occur.
    Materialart: Digitale Medien
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  • 86
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1789-1795 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The recently introduced annihilated unrestricted Hartree–Fock (AUHF) wave function—in which the first spin contaminant in an unrestricted Hartree–Fock (UHF) wave function has been annihilated self-consistently—is discussed in some detail with particular attention to its use as a basis for a perturbation expansion. A series of calculations are presented highlighting the advantages and disadvantages of a second-order Møller–Plesset (AUMP2) perturbation treatment.
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  • 87
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1813-1823 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: A study is made of the vibrational energy levels and the corresponding oscillation dynamics of the clusters Xe4He2, Xe3He2, and I24He. XeHe2 is a representative of the "three ball'' clusters, while I2He is a prototype of the "stick and ball'' systems. The treatment is based on the vibrational self-consistent field (SCF) method, which introduces an approximate separation of the modes involved. Success of the method depends on an adequate choice of the coordinates that are being mutually separated. We use physical arguments, based on mass ratios and potential function considerations, as well as comparative SCF calculations in different coordinate systems, to determine the appropriate modes for each system. Numerically exact results are also obtained by configuration interaction (CI) calculations using a basis of SCF states. The SCF and CI calculations include all modes and employ realistic potentials. Several states that are both rotationally and vibrationally excited are also calculated. The main conclusions are: (1) Hyperspherical coordinates are the best modes for XeHe2; ellipsoidal coordinates are best for I2He. In each case, the "good modes'' SCF gives energies in remarkable agreement with the exact (CI) ones. (2) XeHe2 resembles a quantum liquid drop: Even in the ground state, it is delocalized over and between the (two) classical equilibrium structures. (3) Structural distributions, rather than rigid geometry, are essential for the description of such floppy clusters. The single-mode SCF wave functions offer a highly accurate description of the structural distributions. (4) There is a sequence of bound, excited rotational states of I2He in which the He precesses around the I2 axis. The amplitude of the I2He bending vibrations are very large (θA〈20°), but none of the bound states involves a full rotational motion around the I2 stick (with angular momentum normal to the axis). The SCF method with the "good coordinates'' proposed here is expected to yield results of similar high accuracy for any cluster of the "three balls'' or "stick and ball'' types.
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  • 88
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1702-1705 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: A new implementation of the complex coordinate method is presented. It is a combination of the stabilization method with the partitioning technique, supplemented with the idea of dilation-adapted basis sets. This method is designed to handle large scale calculations of many-electron resonant states, as to minimize the amount of complex arithmetics and in particular to avoid the diagonalization of the complex eigenvalue problem. Both a resonant eigenvalue and a corresponding eigenvector are obtained. An application to the lowest doubly excited autoionizing states of helium is presented.
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  • 89
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1918-1925 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: We use the mean field theory of Pink et al. with the ab initio calculations of the density of states of Tevlin et al. to calculate various features of the main phase transition of a lipid bilayer using fewer fitting parameters than in previous models. Good agreement with experiment is obtained for the calculated transition temperature, Gibbs free energy, enthalpy, and average number of gauche rotations per acyl chain. The average chain area is poorly predicted; we expect this to be corrected once cooperative packing of the acyl chains is taken into account. The nematic order along the chain is also calculated and found to agree qualitatively with experiment.
    Materialart: Digitale Medien
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  • 90
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1938-1940 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 91
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1937-1938 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The photoreduction of CH3Cl was used to detect the transmission of electrons through layers of H2O and Xe on Ni(111) under ultrahigh vacuum (UHV) conditions. At a laser wavelength of 248 nm with H2O spacers, the electron intensity exhibited a nearly exponential decay to zero signal with the 1/e point at about 2 monolayers. At 193 nm with H2O spacers, the signal decayed with the 1/e point at about 4 monolayers to a constant value due to the direct photofragmentation of the CH3 Cl possible at this wavelength. At 248 nm with Xe spacers, the signal decayed by a factor of 4 in the first 2 monolayers, after which the signal was nearly constant and nonzero for at least 64 monolayers, indicating a long electron mean free path. CH3Br is shown to behave similarly with H2 O spacers at 248 nm.
    Materialart: Digitale Medien
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  • 92
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1944-1945 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: We observed for the first time in an optical high resolution experiment (fluorescence line narrowing) the coupling of low frequency adsorbate motions to vibronic bands of the electronic transition of quinizarin adsorbed on γ-alumina. These motions may provide an important dephasing mechanism for the electronic excitation of absorbed molecules. The increased hole width of adsorbed dyes which is several times larger than in amorphous hosts is thought to be caused by these low frequency modes.
    Materialart: Digitale Medien
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  • 93
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1012-1014 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Oxalic acid can produce oscillations in the Belousov–Zhabotinsky-type reaction in a closed batch system without a mechanism for bromine removal. The stirring rate has a significant effect on the reaction.
    Materialart: Digitale Medien
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  • 94
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1631-1642 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: In this paper we explore the interrelationship between the energetics and the thermodynamic properties of molecular clusters. We advance simple models for the energy spectrum, which are used to derive analytical results for the thermodynamic properties of these clusters. The energy spectrum is characterized by the distribution of the energies of the local minima of the nuclear potential energy hypersurface, i.e., the inherent structures. On each of these energy levels the vibrational density of states of the particular inherent structure is superimposed. The energy spectra were specified in terms of the energy gap, Δ, between the (single) ground state and the excited-state inherent structures, the number, R, of the inherent structures and their energetic spread W. Four classes of energy spectra were considered. (1) A large energy gap with nearly degenerate excited-state manifold, i.e., Δ(very-much-greater-than)W. (2) A large energy gap with a considerable spread of the excited-state manifold, i.e., Δ(very-much-less-than)W and W/R(very-much-less-than)Δ. (3) A gapless spectrum with W/R(approximately-greater-than)Δ. (4) A multiple bunched spectrum with several energy gaps. Explicit analytical relations for the temperature dependence of the internal energy were derived for energy spectra of types (1), (2), and (3) both for the canonical and for the microcanonical ensembles. For energy spectra of types (1) and (2) the caloric curve exhibits a single inflection, which marks the "transition''. A unified description of multistate isomerization with large R, which corresponds to rare-gas clusters, and of molecular isomerization with R(approximately-equal-to)1, which prevails for alkali-halide clusters, was provided. For energy spectra of type (3) the transition disappears, while for energy spectra of type (4) hierarchical isomerization is exhibited. Our analytical models have established the ensemble dependence of the transition for types (1) and (2), which is manifested by a considerable broadening of the transition range for the canonical ensemble, reflecting the role of energy fluctuations in the finite system.
    Materialart: Digitale Medien
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  • 95
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5694-5700 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The photopolymerization properties and the surface pressure dependence of excitonic absorption of polydiacetylene (PDA), i.e., poly-(heptacosa-10,12-diynoic acid), are investigated by in situ reflection spectra of a monolayer at a N2 gas–water (pure water, CdCl2 aqueous solution) interface. The electronic structure of the initially appearing PDA is strongly dependent on the packing condition of diacetylene monomer, the blue- and red-form PDAs that initially appear in loose and close packing conditions, respectively. A reversible color change induced by a change in surface pressure is found for the first time in a partially polymerized PDA monolayer on pure water, in which blue and red form PDAs appear predominantly at low and high surface pressures, respectively. Further, two metastable phases, observed at wavelengths about 40 nm longer than those of the blue form, are thought to be induced by the rheological process of the substitutional sidegroups. Our results suggest that these color changes are closely related to a strain on the acetylenic backbone structure which is induced by the deformation of substitutional alkyl sidegroups.
    Materialart: Digitale Medien
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  • 96
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5701-5706 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The adsorption of NO on Ag(111) at 80 K has been studied by high resolution electron energy loss spectroscopy (HREELS) and thermal desorption spectroscopy (TDS). At low exposures (≤0.05 L) NO is adsorbed in part dissociatively and in part molecularly in two different threefold bridge states (in upright and bent or tilted orientation with respect to the surface normal). The NO molecules in the threefold bridge position are desorbed at 100 K. With increasing exposure the desorption temperature shifts gradually to 110 K. At medium exposures (∼0.13 L) additional NO is adsorbed molecularly in an atop position with an upright orientation in admixture with atomic N and O and molecular NO adsorbed in threefold bridge states. The NO molecules adsorbed in atop position are weakly bonded on the surface and are desorbed at about 90 K. Simultaneously, N2O is formed and adsorbed on the surface. At saturation a new bent or tilted NO species in atop position appears on the surface and the amount of N2O significantly increases. The N2O molecules are desorbed at 90, 110, and 190 K. At saturation all the NO and NO-derived species (the threefold bridge and atop states, N2O and atomic oxygen and nitrogen) coexist on Ag(111).
    Materialart: Digitale Medien
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  • 97
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1762-1774 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Nonrelativistic and relativistic Hartree–Fock (HF) and configuration interaction (CI) calculations have been performed in order to analyze the relativistic and correlation effects in various diatomic gold compounds. It is found that relativistic effects reverse the trend in most molecular properties down the group (11). The consequences for gold chemistry are described. Relativistic bond stabilizations or destabilizations are dependent on the electronegativity of the ligand, showing the largest bond destabilization for AuF (86 kJ/mol at the CI level) and the largest stabilization for AuLi (−174 kJ/mol). Relativistic bond contractions lie between 1.09 (AuH+) and 0.16 A(ring) (AuF). Relativistic effects of various other properties are discussed. A number of as yet unmeasured spectroscopic properties, such as bondlengths (re), dissociation energies (De), force constants (ke), and dipole moments (μe), are predicted.
    Materialart: Digitale Medien
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  • 98
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1783-1788 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Geometry optimizations and band structure calculations are reported on two polymeric vinylene derivatives of pyrene: poly(1,6-pyrenylene vinylene) and poly(2,7-pyrenylene vinylene). The results are indicative of a dramatic sensitivity of the electronic structure on the mode of connection of the two vinylene units to the pyrene rings, in agreement with the chemist's intuition. An analysis of the atomic π orbital contributions to the one-electron wave functions shows that the HOMO–LUMO characteristics of both compounds are markedly different. The 1-6 mode of connection leads to an electronic structure similar to that of polyparaphenylene with a bandgap of 2.9 eV. The 2-7 mode of connection results in a significantly lower bandgap, around 1.7 eV, due to the stabilization of quinoid resonance structures.
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  • 99
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1796-1812 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: A theoretical study of the relationship between interatomic distances and the spectral positions of valence- and K-shell σ* photoionization resonances is reported for a selected series of molecules. Three-dimensional graphical representations of the occupied and virtual-valence σ-symmetry orbitals of these compounds reveal their striking similarity to the wave functions of a particle in a cylindrical well, substantiating qualitative notions long employed in free-electron molecular orbital (FEMO) approximations. Accordingly, the molecular potential along the symmetry axis in these compounds is modeled after a finite square well, with a depth approximately equal to the energy of the lowest σ-symmetry valence molecular orbital and a width determined from analogies to FEMO theory. Calculated minimal-basis-set molecular-orbital energies for both occupied and virtual states are seen to correlate accurately with the simple square-well energy level formula (π2 /2)(n2/l 2 ) when measured in Hartree atomic units from the bottom of the well. The calculated σ* orbital energies are furthermore in excellent agreement with experimentally and theoretically determined valence-shell photoionization resonance positions, the latter consequently also satisfying the square-well correlation formula. A similar situation obtains for experimentally and theoretically determined K-shell resonance positions, although energy shifts from minimal-basis values are evident in these cases. These circumstances are clarified quantitatively on basis of Feshbach–Fano considerations, in which minimal-basis-set virtual-valence σ* orbitals play the roles of zeroth-order states subject to modification by interactions with nonresonant background continua. Concluding remarks contrast and compare molecular-orbital and square-well approaches to photoionization resonances with those based on multiple-scattering and barrier models. The present results appear to clarify the origins of recently reported empirical correlations of bond lengths with resonance positions, and help to determine their range of applicability.
    Materialart: Digitale Medien
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  • 100
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1866-1874 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The viscosity of a suspension of spherical Brownian particles is determined by Stokesian dynamics as a function of the Péclet number. Several new aspects concerning the theoretical derivation of the direct contribution of the Brownian motion to the bulk stress are given, along with the results obtained from a simulation of a monolayer. The simulations reproduce the experimental behavior generally observed in dense suspensions, and an explanation of this behavior is given by observing the evolution of the different contributions to the viscosity with shear rate. The shear thinning at low Péclet numbers is due to the disappearance of the direct Brownian contribution to the viscosity; the deformation of the equilibrium microstructure is, however, small. By contrast, at very high Péclet numbers the suspension shear thickens due to the formation of large clusters.
    Materialart: Digitale Medien
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