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  • American Institute of Physics (AIP)  (81,592)
  • PANGAEA  (42,943)
  • 2020-2024  (34,429)
  • 1995-1999  (56,154)
  • 1985-1989  (33,275)
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  • 1
    Publication Date: 2023-01-30
    Description: Despite the importance of surface energy budgets (SEBs) for land-climate interactions in the Arctic, uncertainties in their prediction persist. In situ observational data of SEB components - useful for research and model validation - are collected at relatively few sites across the terrestrial Arctic, and not all available datasets are readily interoperable. Furthermore, the terrestrial Arctic consists of a diversity of vegetation types, which are generally not well represented in land surface schemes of current Earth system models. This dataset describes the data generated in a literature synthesis, covering 358 study sites on vegetation or glacier (〉=60°N latitude), which contained surface energy budget observations. The literature synthesis comprised 148 publications searched on the ISI Web of Science Core Collection.
    Language: English
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  • 2
    Publication Date: 2023-01-27
    Description: Organic carbon (OC) stored in Arctic permafrost represents one of Earth's largest and most vulnerable terrestrial carbon pools. Amplified climate warming across the Arctic results in widespread permafrost thaw. Permafrost deposits exposed at river cliffs and coasts are particularly susceptible to thawing processes. Accelerating erosion of terrestrial permafrost along shorelines leads to increased transfer of organic matter (OM) to nearshore waters. However, the amount of terrestrial permafrost carbon and nitrogen as well as the OM quality in these deposits are still poorly quantified. Here, we characterise the sources and the quality of OM supplied to the Lena River at a rapidly eroding permafrost river shoreline cliff in the eastern part of the delta (Sobo-Sise Island). Our multi-proxy approach captures bulk elemental, molecular geochemical and carbon isotopic analyses of late Pleistocene Yedoma permafrost and Holocene cover deposits, discontinuously spanning the last ~52 ka. We show that the ancient permafrost exposed in the Sobo-Sise cliff has a high organic carbon content (mean of about 5 wt%).We found that the OM quality, which we define as the intrinsic potential to further transformation, decomposition, and mineralization, is also high as inferred by the lipid biomarker inventory. The oldest sediments stem from Marine Isotope Stage (MIS) 3 interstadial deposits (dated to 52 to 28 cal kyr BP) and is overlaid by Last Glacial MIS 2 (dated to 28 to 15 cal ka BP) and Holocene MIS 1 (dated to 7–0 cal ka BP) deposits. The relatively high average chain length (ACL) index of n-alkanes along the cliff profile indicates a predominant contribution of vascular plants to the OM composition. The elevated ratio of iso and anteiso-branched FAs relative to long chain (C ≥ 20) n-FAs in the interstadial MIS 3 and the interglacial MIS 1 deposits, suggests stronger microbial activity and consequently higher input of bacterial biomass during these climatically warmer periods. The overall high carbon preference index (CPI) and higher plant fatty acid (HPFA) values as well as high C / N ratios point to a good quality of the preserved OM and thus to a high potential of the OM for decomposition upon thaw. A decrease of HPFA values downwards along the profile probably indicates a relatively stronger OM decomposition in the oldest (MIS 3) deposits of the cliff.
    Language: English
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  • 3
    Publication Date: 2023-08-25
    Description: Surface air temperature measurements obtained from different sensors are used to construct a unique time series with one minute time-interval. Apart from differences in design and environmental exposition, periods of missing data also exist in the data series of each sensor. A primary data set was selected in terms of quality and temporal extension. A combination of two different techniques is applied to complete this data set: one is based on the autocorrelation of the series and the other on measurements taken from other sensors. The resulting values constitute a complete series of surface air temperature at AGGO.
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  • 4
    Publication Date: 2023-02-09
    Description: The rewetting of peatlands is a promising measure to mitigate greenhouse gas (GHG) emissions by preventing the further mineralization of the peat soil through aeration. In coastal peatland, the rewetting with brackish water can increase the GHG mitigation potential by the introduction of sulfate, a terminal electron acceptor (TEA). Sulfate is known to lower the CH4 production and thus, its emission by favoring the growth of sulfate-reducers, which outcompete methanogens for substrate. The data contain porewater variables such as pH, electrical conductivity (EC) and sulfate, chloride, dissolved CO2 and CH4 concentrations, as well as absolute abundances of methane- and sulfate-cycling microbial communities. The data were collected in spring and autumn 2019 after a storm surge with brackish water inflow in January 2019. Field sampling was conducted in the nature reserve Heiligensee and Hütelmoor in North-East Germany, close to the Southern Baltic Sea coast. We took peat cores using a Russian peat corer in addition to pore water diffusion samplers and plastic liners (length: 60cm; inner diameter 10 cm) at four locations along a transect from further inland towards the Baltic Sea. We wanted to compare the soil and pore water geochemistry as well as the microbial communities after the brackish water inflow to the common freshwater rewetting state. Pore water was extracted using pore water suction samplers in the lab and environmental variables were quantified with an ICP. Microbial samples were sampled from the peat core using sterile equipment. We used quantitative polymerase chain reaction (qPCR) to characterize pools of DNA and cDNA targeting total and putatively active bacteria and archaea. qPCR was performed on key functional genes of methane production (mcrA), aerobic methane oxidation (pmoA) and sulfate reduction (dsrB) in addition to the 16S rRNA gene for the absolute abundance of total prokaryotes. Furthermore, we retrieved soil plugs to determine the concentrations and isotopic signatures of dissolved trace gases (CO2/DIC and CH4) in the pore water.
    Language: English
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  • 5
    Publication Date: 2023-01-30
    Description: This dataset provides annually resolved microfacies data from ICDP core 5017-1-A, retrieved from the deep northern Dead Sea basin in 2010/11, for the last glacial-interglacial transition (ca. 14-13 ka BP). Sediments of the Lisan Formation were investigated between ~94.7 and 91.8 m sediment depth below lake floor (lithozone C2) by continuous thin section microscopy. Thin sections were prepared following the standard procedure by Brauer and Casanova (2001) that was adjusted for salty sediments. Thin section analyses were performed on overlapping large-scale thin sections using a Zeiss Axiolab pol microscope at magnifications of 50-400x. Microfacies analyses included varve counting and measurements of varve and sublayer thickness. The amount of varves in erosional gaps was interpolated and the position of mass flow deposits (MFD) is marked.
    Language: English
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  • 6
    Publication Date: 2023-01-30
    Description: We present sea ice temperature and salinity data from first-year ice (FYI) and second-year ice (SYI) relevant to the temporal development of sea ice permeability and brine drainage efficiency from the early growth phase in October 2019 to the onset of spring warming in May 2020. Our dataset was collected in the central Arctic Ocean during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) Expedition in 2019 to 2020. MOSAiC was an international transpolar drift expedition in which the German icebreaker RV Polarstern anchored into an ice floe to gain new insights into Arctic climate over a full annual cycle. In October 2019, RV Polarstern moored to an ice floe in the Siberian sector of the Arctic at 85 degrees north and 137 degrees east to begin the drift towards the North Pole and the Fram Strait via the Transpolar Drift Stream. The data presented here were collected during the first three legs of the expedition, so all the coring activities took place on the same floe. The end dates of legs 1, 2, and 3 were 13 December, 24 February, and 4 June, respectively. The dataset contributed to a baseline study entitled, Deciphering the properties of different Arctic ice types during the growth phase of the MOSAiC floes: Implications for future studies. The study highlights downward directed gas pathways in FYI and SYI by inferring sea ice permeability and potential brine release from several time series of temperature and salinity measurements. The physical properties presented in this paper lay the foundation for subsequent analyses on actual gas contents measured in the ice cores, as well as air-ice and ice-ocean gas fluxes. Sea ice cores were collected with a Kovacs Mark II 9 cm diameter corer. To measure ice temperatures, about 4.5 cm deep holes were drilled into the core (intervals varied by site and leg) . The temperatures were measured by a digital thermometer within minutes after the cores were retrieved. The ice cores were placed into pre-labelled plastic sleeves sealed at the bottom end. The ice cores were transported to RV Polarstern and stored in a -20 degrees Celsius freezer. Each of the cores was sub-sampled, melted at room temperature, and processed for salinity within one or two days. The practical salinity was estimated by measuring the electrical conductivity and temperature of the melted samples using a WTW Cond 3151 salinometer equipped with a Tetra-Con 325 four-electrode conductivity cell. The practical salinity represents the the salinity estimated from the electrical conductivity of the solution. The dataset also contains derived variables, including sea ice density, brine volume fraction, and the Rayleigh number.
    Language: English
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  • 7
    Publication Date: 2023-01-30
    Description: Organic carbon (OC) stored in Arctic permafrost represents one of Earth’s largest and most vulnerable terrestrial carbon pools. Amplified climate warming across the Arctic results in widespread permafrost thaw. Permafrost deposits exposed at river cliffs and coasts are particularly susceptible to thawing processes. Accelerating erosion of terrestrial permafrost along shorelines leads to increased transfer of organic matter (OM) to nearshore waters. However, the amount of terrestrial permafrost carbon and nitrogen as well as the OM quality in these deposits are still poorly quantified. Here, we characterise the sources and the quality of OM supplied to the Lena River at a rapidly eroding permafrost river shoreline cliff in the eastern part of the delta (Sobo-Sise Island). Our multi-proxy approach captures bulk elemental, molecular geochemical and carbon isotopic analyses of late Pleistocene Yedoma permafrost and Holocene cover deposits, discontinuously spanning the last ~52 ka. We show that the ancient permafrost exposed in the Sobo-Sise cliff has a high organic carbon content (mean of about 5 wt%).We found that the OM quality, which we define as the intrinsic potential to further transformation, decomposition, and mineralization, is also high as inferred by the lipid biomarker inventory. The oldest sediments stem from Marine Isotope Stage (MIS) 3 interstadial deposits (dated to 52 to 28 cal kyr BP) and is overlaid by Last Glacial MIS 2 (dated to 28 to 15 cal ka BP) and Holocene MIS 1 (dated to 7–0 cal ka BP) deposits. The relatively high average chain length (ACL) index of n-alkanes along the cliff profile indicates a predominant contribution of vascular plants to the OM composition. The elevated ratio of iso and anteiso-branched FAs relative to long chain (C ≥ 20) n-FAs in the interstadial MIS 3 and the interglacial MIS 1 deposits, suggests stronger microbial activity and consequently higher input of bacterial biomass during these climatically warmer periods. The overall high carbon preference index (CPI) and higher plant fatty acid (HPFA) values as well as high C / N ratios point to a good quality of the preserved OM and thus to a high potential of the OM for decomposition upon thaw. A decrease of HPFA values downwards along the profile probably indicates a relatively stronger OM decomposition in the oldest (MIS 3) deposits of the cliff.
    Language: English
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  • 8
    Publication Date: 2023-01-30
    Description: We present sea ice temperature and salinity data from first-year ice (FYI) and second-year ice (SYI) relevant to the temporal development of sea ice permeability and brine drainage efficiency from the early growth phase in October 2019 to the onset of spring warming in May 2020. Our dataset was collected in the central Arctic Ocean during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) Expedition in 2019 to 2020. MOSAiC was an international transpolar drift expedition in which the German icebreaker RV Polarstern anchored into an ice floe to gain new insights into Arctic climate over a full annual cycle. In October 2019, RV Polarstern moored to an ice floe in the Siberian sector of the Arctic at 85 degrees north and 137 degrees east to begin the drift towards the North Pole and the Fram Strait via the Transpolar Drift Stream. The data presented here were collected during the first three legs of the expedition, so all the coring activities took place on the same floe. The end dates of legs 1, 2, and 3 were 13 December, 24 February, and 4 June, respectively. The dataset contributed to a baseline study entitled, Deciphering the properties of different Arctic ice types during the growth phase of the MOSAiC floes: Implications for future studies. The study highlights downward directed gas pathways in FYI and SYI by inferring sea ice permeability and potential brine release from several time series of temperature and salinity measurements. The physical properties presented in this paper lay the foundation for subsequent analyses on actual gas contents measured in the ice cores, as well as air-ice and ice-ocean gas fluxes. Sea ice cores were collected with a Kovacs Mark II 9 cm diameter corer. To measure ice temperatures, about 4.5 cm deep holes were drilled into the core (intervals varied by site and leg) . The temperatures were measured by a digital thermometer within minutes after the cores were retrieved. The ice cores were placed into pre-labelled plastic sleeves sealed at the bottom end. The ice cores were transported to RV Polarstern and stored in a -20 degrees Celsius freezer. Each of the cores was sub-sampled, melted at room temperature, and processed for salinity within one or two days. The practical salinity was estimated by measuring the electrical conductivity and temperature of the melted samples using a WTW Cond 3151 salinometer equipped with a Tetra-Con 325 four-electrode conductivity cell. The practical salinity represents the the salinity estimated from the electrical conductivity of the solution. The dataset also contains derived variables, including sea ice density, brine volume fraction, and the Rayleigh number.
    Language: English
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  • 9
    Publication Date: 2023-01-30
    Description: These datasets describe sediment samples taken from the Batagay megaslump, located in Yana Uplands in northeastern Siberia. Most sediment samples were taken from the slump headwall (B19-P1) by rapelling down on a rope from the slump surface and taking samples with a hole saw (diameter 55 mm, 40 mm deep) mounted on a handheld power drill. A second profile (B19-02) of the lowest part of the slump headwall was sampled (~100 m south) using a hammer and axe from the slump floor. Two permafrost sediment blocks (B19-03 and B19-04) at the slump bottom that had fallen from the headwall were sampled using a chainsaw. Finally, a baidzherakh (thermokarst mound; B19-05) in the north of the slump was sampled using a hammer and axe. The samples cover 5 stratigraphical units: 1. lower ice complex, 2. lower sand unit, 3. woody layer, 4. upper ice complex, 5. Holocene cover.
    Language: English
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  • 10
    Publication Date: 2023-01-30
    Description: Organic carbon (OC) stored in Arctic permafrost represents one of Earth’s largest and most vulnerable terrestrial carbon pools. Amplified climate warming across the Arctic results in widespread permafrost thaw. Permafrost deposits exposed at river cliffs and coasts are particularly susceptible to thawing processes. Accelerating erosion of terrestrial permafrost along shorelines leads to increased transfer of organic matter (OM) to nearshore waters. However, the amount of terrestrial permafrost carbon and nitrogen as well as the OM quality in these deposits are still poorly quantified. Here, we characterise the sources and the quality of OM supplied to the Lena River at a rapidly eroding permafrost river shoreline cliff in the eastern part of the delta (Sobo-Sise Island). Our multi-proxy approach captures bulk elemental, molecular geochemical and carbon isotopic analyses of late Pleistocene Yedoma permafrost and Holocene cover deposits, discontinuously spanning the last ~52 ka. We show that the ancient permafrost exposed in the Sobo-Sise cliff has a high organic carbon content (mean of about 5 wt%).We found that the OM quality, which we define as the intrinsic potential to further transformation, decomposition, and mineralization, is also high as inferred by the lipid biomarker inventory. The oldest sediments stem from Marine Isotope Stage (MIS) 3 interstadial deposits (dated to 52 to 28 cal kyr BP) and is overlaid by Last Glacial MIS 2 (dated to 28 to 15 cal ka BP) and Holocene MIS 1 (dated to 7–0 cal ka BP) deposits. The relatively high average chain length (ACL) index of n-alkanes along the cliff profile indicates a predominant contribution of vascular plants to the OM composition. The elevated ratio of iso and anteiso-branched FAs relative to long chain (C ≥ 20) n-FAs in the interstadial MIS 3 and the interglacial MIS 1 deposits, suggests stronger microbial activity and consequently higher input of bacterial biomass during these climatically warmer periods. The overall high carbon preference index (CPI) and higher plant fatty acid (HPFA) values as well as high C / N ratios point to a good quality of the preserved OM and thus to a high potential of the OM for decomposition upon thaw. A decrease of HPFA values downwards along the profile probably indicates a relatively stronger OM decomposition in the oldest (MIS 3) deposits of the cliff.
    Language: English
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  • 11
    Publication Date: 2023-01-30
    Language: English
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  • 12
    Publication Date: 2023-01-30
    Description: We present sea ice temperature and salinity data from first-year ice (FYI) and second-year ice (SYI) relevant to the temporal development of sea ice permeability and brine drainage efficiency from the early growth phase in October 2019 to the onset of spring warming in May 2020. Our dataset was collected in the central Arctic Ocean during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) Expedition in 2019 to 2020. MOSAiC was an international transpolar drift expedition in which the German icebreaker RV Polarstern anchored into an ice floe to gain new insights into Arctic climate over a full annual cycle. In October 2019, RV Polarstern moored to an ice floe in the Siberian sector of the Arctic at 85 degrees north and 137 degrees east to begin the drift towards the North Pole and the Fram Strait via the Transpolar Drift Stream. The data presented here were collected during the first three legs of the expedition, so all the coring activities took place on the same floe. The end dates of legs 1, 2, and 3 were 13 December, 24 February, and 4 June, respectively. The dataset contributed to a baseline study entitled, Deciphering the properties of different Arctic ice types during the growth phase of the MOSAiC floes: Implications for future studies. The study highlights downward directed gas pathways in FYI and SYI by inferring sea ice permeability and potential brine release from several time series of temperature and salinity measurements. The physical properties presented in this paper lay the foundation for subsequent analyses on actual gas contents measured in the ice cores, as well as air-ice and ice-ocean gas fluxes. Sea ice cores were collected with a Kovacs Mark II 9 cm diameter corer. To measure ice temperatures, about 4.5 cm deep holes were drilled into the core (intervals varied by site and leg) . The temperatures were measured by a digital thermometer within minutes after the cores were retrieved. The ice cores were placed into pre-labelled plastic sleeves sealed at the bottom end. The ice cores were transported to RV Polarstern and stored in a -20 degrees Celsius freezer. Each of the cores was sub-sampled, melted at room temperature, and processed for salinity within one or two days. The practical salinity was estimated by measuring the electrical conductivity and temperature of the melted samples using a WTW Cond 3151 salinometer equipped with a Tetra-Con 325 four-electrode conductivity cell. The practical salinity represents the the salinity estimated from the electrical conductivity of the solution. The dataset also contains derived variables, including sea ice density, brine volume fraction, and the Rayleigh number.
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  • 13
    Publication Date: 2023-01-30
    Description: Rock magnetic and paleomagnetic results covering the past 30 ka were constructed from two sediment cores MSM33_856-1 (MSM33-55-1) and MSM33_855-1 (54-3) from the Black Sea. After the Mediterranean Sea water ingression, finely laminated organic-rich sapropelic sediments and coccolith oozes were deposited in the Black Sea since about 8.3 ka. Relict magnetic minerals in the Black Sea sarpoples are ferrous hemoilmenite, Fe-Mn and Fe-Cr spinels, and magnetite inclusions. In sediments deposited between about 14 and 8 ka, greigite and pyrite were formed in sediments because of the seawater penetration from overlying sediments after the seawater ingression. Before ~14 ka, the Black Sea sediments are dominated by detrital (titano-)magnetite minerals and the sporadically formed greigite which has SIRM/kLF ratios 〉 10 kAm-2. By comparison with detrital (titano-)magnetite samples between 20-30 ka, we found that relict magnetic mineral samples between 0-8.3 ka have similar behavior in recording the geomagnetic field. Moreover, the geomagnetic field variations reconstructed from the Black Sea sapropels are comparable with other validated regional datasets for the past 8.3 ka. The natural remanent magnetization (NRM) and the anhysteretic remanent magnetization (ARM) were measured with a 2G Enterprises 755 SRM (cryogenic) long-core magnetometer equipped with a sample holder for eight discrete samples at a separation of 20 cm. The magnetometer's in-line tri-axial alternating field (AF) demagnetizer was used to demagnetize the NRM and ARM of the samples. The NRM was measured after application of AF peak amplitudes of 0, 5, 10, 15, 20, 30, 40, 50, 65, 80, and 100 mT. Directions of the characteristic remanent magnetization (ChRM) were determined by principle component analysis (PCA) according to Kirschvink (1980). The error range of the ChRM is given as the maximum angular deviation (MAD). The ARM was imparted along the samples' z-axis with a static field of 0.05 mT and an AF field of 100 mT. Demagnetization then was performed in steps of 0, 10, 20, 30, 40, 50, 65, and 80 mT. The median destructive field of the ARM (MDFARM) was determined to estimate the coercivity of the sediments. The slope of NRM versus ARM of common demagnetization steps was used to determine the relative paleointensity (RPI). In most cases, demagnetization steps from 20 to 65 mT were used to determine the RPI.
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  • 14
    Publication Date: 2023-01-30
    Description: This dataset provides data for four third-degree tidal constituents used in the publication of Sulzbach et al (2022). The tidal constituents provided are the 3M1, 3M3, 3N2 and 3L2 for 134 globally distributed stations. The tide information, such as the nodal modulations of these tides, are taken from Table 1 and Table S2 of Ray (2020). These tidal constants are estimated using the GESLA dataset (Woodworth et al 2014) following the approach presented in Piccioni et al (2019). This record is an add-on to the full TICON dataset (https://doi.org/10.1594/PANGAEA.896587), using exactly the same data format and pre-processing. These steps include using tide gauge data that contains at least ten years of continuous data. Further, the dataset is restricted to only contain open ocean tide gauges by limiting it to a mean surrounding depth of tide gauges to be deeper than 500 meters in a 2-degree radius and excluding stations not native to the ocean domain of the employed tidal model TiME. Duplicate and closely neighbouring tide gauges, found within a 0.2-degree radius, are also removed from the dataset. This resulted in the availability of the four tidal constants for 134 tide gauges. The results are stored in one tab-separated text/ASCII file with 13 columns: 1. Latitude of the tide gauge station 2. Longitude of the tide gauge station 3. Constituent name 4. Amplitude (in cm) 5. Phase (in degrees) 6. Standard deviation of the amplitude (in cm) 7. Standard deviation of the phase (in degrees) 8. Percentage of missing observations 9. Total number of observations analyzed 10. Length of the maximum temporal gap found in the time series in days 11. Date of the first observation 12. Date of the last observation 13. Code that corresponds to the original source of the record TICON is a useful and easy-to-handle data set for tide model validation and allows the users to select the records according to the different criteria most suitable for their purposes. The options span from the choice of a geographical region to the use of single constituents or time periods.
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  • 15
    Publication Date: 2023-01-30
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  • 16
    Publication Date: 2023-01-30
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  • 17
    Publication Date: 2023-01-30
    Description: These datasets provide sedimentological data partly at annual resolution and an age model for the lateglacial part of (1) the ICDP sediment core 5017-1-A retrieved from the deep northern Dead Sea basin in 2010/11, and (2) for the Masada outcrop located at the southwestern shore of the Dead Sea sampled in 2018. The here investigated two sediment sections cover the last glacial-interglacial transition (ca. 17-11.5 ka BP) in the hydroclimatically sensitive Levant, when the water level of Lake Lisan – the precursor of the Dead Sea – dropped dramatically from its glacial high-stand to the Holocene low levels. Here, we analyze the interval between the last two gypsum units – the Upper Gypsum Unit (UGU) and the Additional Gypsum Unit (AGU) – which were also used to correlate the two sites. In the ICDP core this section is located between ~101 and 88.5 m sediment depth below lake floor and at Masada it encompasses the uppermost ~3.8 m sediments of the Lisan Formation, which form the terminal deposit at this site. Due to the lake level decline, the complete transition into the Holocene is only recorded in the ICDP core, while sedimentation at Masada terminates earlier. The microfacies was investigated by continuous thin section microscopy, while additional macroscopic information is provided from over- and underlying sediment sections. A revised chronology using age modelling in OxCal (Ramsey 2008; Ramsey 2009; Ramsey and Lee 2013) was developed for the ICDP core and a floating varve chronology was constructed at Masada. Using these new microfacies data from marginal (Masada) and deep-water (ICDP core) sediments, the hydroclimatic variability during the final stage of Lake Lisan can be reconstructed, which could provide important insights into the development of human sedentism in the region at this time.
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  • 18
    Publication Date: 2023-01-30
    Description: We present sea ice temperature and salinity data from first-year ice (FYI) and second-year ice (SYI) relevant to the temporal development of sea ice permeability and brine drainage efficiency from the early growth phase in October 2019 to the onset of spring warming in May 2020. Our dataset was collected in the central Arctic Ocean during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) Expedition in 2019 to 2020. MOSAiC was an international transpolar drift expedition in which the German icebreaker RV Polarstern anchored into an ice floe to gain new insights into Arctic climate over a full annual cycle. In October 2019, RV Polarstern moored to an ice floe in the Siberian sector of the Arctic at 85 degrees north and 137 degrees east to begin the drift towards the North Pole and the Fram Strait via the Transpolar Drift Stream. The data presented here were collected during the first three legs of the expedition, so all the coring activities took place on the same floe. The end dates of legs 1, 2, and 3 were 13 December, 24 February, and 4 June, respectively. The dataset contributed to a baseline study entitled, Deciphering the properties of different Arctic ice types during the growth phase of the MOSAiC floes: Implications for future studies. The study highlights downward directed gas pathways in FYI and SYI by inferring sea ice permeability and potential brine release from several time series of temperature and salinity measurements. The physical properties presented in this paper lay the foundation for subsequent analyses on actual gas contents measured in the ice cores, as well as air-ice and ice-ocean gas fluxes. Sea ice cores were collected with a Kovacs Mark II 9 cm diameter corer. To measure ice temperatures, about 4.5 cm deep holes were drilled into the core (intervals varied by site and leg) . The temperatures were measured by a digital thermometer within minutes after the cores were retrieved. The ice cores were placed into pre-labelled plastic sleeves sealed at the bottom end. The ice cores were transported to RV Polarstern and stored in a -20 degrees Celsius freezer. Each of the cores was sub-sampled, melted at room temperature, and processed for salinity within one or two days. The practical salinity was estimated by measuring the electrical conductivity and temperature of the melted samples using a WTW Cond 3151 salinometer equipped with a Tetra-Con 325 four-electrode conductivity cell. The practical salinity represents the the salinity estimated from the electrical conductivity of the solution. The dataset also contains derived variables, including sea ice density, brine volume fraction, and the Rayleigh number.
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  • 19
    Publication Date: 2023-01-30
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  • 20
    Publication Date: 2023-01-30
    Description: This dataset provides annually resolved microfacies data from ICDP core 5017-1-A, retrieved from the deep northern Dead Sea basin in 2010/11, for the last glacial-interglacial transition (ca. 17-11.5 ka BP). Sediments of the Lisan Formation were investigated between ~101 and 88.5 m sediment depth below lake floor by continuous thin section microscopy, while additional macroscopic information is provided from core catchers, as well as from over- and underlying sediment sections. Thin sections were prepared following the standard procedure by Brauer and Casanova (2001) that was adjusted for salty sediments. Thin section analyses were performed on overlapping large-scale thin sections using a Zeiss Axiolab pol microscope at magnifications of 50-400x. Microfacies analyses included varve counting and measurements of varve and sublayer thickness.
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  • 21
    Publication Date: 2023-01-30
    Description: Despite the importance of surface energy budgets (SEBs) for land-climate interactions in the Arctic, uncertainties in their prediction persist. In situ observational data of SEB components - useful for research and model validation - are collected at relatively few sites across the terrestrial Arctic, and not all available datasets are readily interoperable. Furthermore, the terrestrial Arctic consists of a diversity of vegetation types, which are generally not well represented in land surface schemes of current Earth system models. This dataset contains metadata information about surface energy budget components measured at 64 tundra and glacier sites 〉60° N across the Arctic. This information was taken from the open-access repositories FLUXNET, Ameriflux, AON, GC-Net and PROMICE. The contained datasets are associated with the publication vegetation type as an important predictor of the Arctic Summer Land Surface Energy Budget by Oehri et al. 2022, and intended to support research of surface energy budgets and their relationship with environmental conditions, in particular vegetation characteristics across the terrestrial Arctic.
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  • 22
    Publication Date: 2023-01-30
    Description: This dataset provides the results from Bayesian age depth modelling in OxCal for ICDP core 5017-1-A, retrieved from the deep northern Dead Sea basin in 2010/11, for the last glacial-interglacial transition between ~101 and 88.5 m sediment depth below lake floor (ca. 17-11.5 ka BP). The model was performed in OxCal v.4.4 using a P_Sequence (1,1,C(-2,2)) (Ramsey 2008; Ramsey 2009; Ramsey and Lee 2013) and includes three tephrochronological ages from Neugebauer et al. (2021) and three radiocarbon ages from Kitagawa et al. (2017).
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  • 23
    Publication Date: 2023-01-30
    Description: Despite the importance of surface energy budgets (SEBs) for land-climate interactions in the Arctic, uncertainties in their prediction persist. In situ observational data of SEB components - useful for research and model validation - are collected at relatively few sites across the terrestrial Arctic, and not all available datasets are readily interoperable. Furthermore, the terrestrial Arctic consists of a diversity of vegetation types, which are generally not well represented in land surface schemes of current Earth system models. This dataset comprises harmonized, standardized and aggregated in-situ observations of surface energy budget components measured at 64 sites on vegetated and glaciated sites north of 60° latitude, in the time period from 1994 till 2021. The surface energy budget components include net radiation, sensible heat flux, latent heat flux, ground heat flux, net shortwave radiation, net longwave radiation, surface temperature and albedo, which were aggregated to daily mean, minimum and maximum values from hourly and half-hourly measurements. Data were retrieved from the monitoring networks FLUXNET, AmeriFlux, AON, GC-Net and PROMICE.
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  • 24
    Publication Date: 2023-01-30
    Description: We present sea ice temperature and salinity data from first-year ice (FYI) and second-year ice (SYI) relevant to the temporal development of sea ice permeability and brine drainage efficiency from the early growth phase in October 2019 to the onset of spring warming in May 2020. Our dataset was collected in the central Arctic Ocean during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) Expedition in 2019 to 2020. MOSAiC was an international transpolar drift expedition in which the German icebreaker RV Polarstern anchored into an ice floe to gain new insights into Arctic climate over a full annual cycle. In October 2019, RV Polarstern moored to an ice floe in the Siberian sector of the Arctic at 85 degrees north and 137 degrees east to begin the drift towards the North Pole and the Fram Strait via the Transpolar Drift Stream. The data presented here were collected during the first three legs of the expedition, so all the coring activities took place on the same floe. The end dates of legs 1, 2, and 3 were 13 December, 24 February, and 4 June, respectively. The dataset contributed to a baseline study entitled, Deciphering the properties of different Arctic ice types during the growth phase of the MOSAiC floes: Implications for future studies. The study highlights downward directed gas pathways in FYI and SYI by inferring sea ice permeability and potential brine release from several time series of temperature and salinity measurements. The physical properties presented in this paper lay the foundation for subsequent analyses on actual gas contents measured in the ice cores, as well as air-ice and ice-ocean gas fluxes. Sea ice cores were collected with a Kovacs Mark II 9 cm diameter corer. To measure ice temperatures, about 4.5 cm deep holes were drilled into the core (intervals varied by site and leg) . The temperatures were measured by a digital thermometer within minutes after the cores were retrieved. The ice cores were placed into pre-labelled plastic sleeves sealed at the bottom end. The ice cores were transported to RV Polarstern and stored in a -20 degrees Celsius freezer. Each of the cores was sub-sampled, melted at room temperature, and processed for salinity within one or two days. The practical salinity was estimated by measuring the electrical conductivity and temperature of the melted samples using a WTW Cond 3151 salinometer equipped with a Tetra-Con 325 four-electrode conductivity cell. The practical salinity represents the the salinity estimated from the electrical conductivity of the solution. The dataset also contains derived variables, including sea ice density, brine volume fraction, and the Rayleigh number.
    Language: English
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  • 25
    Publication Date: 2023-01-30
    Description: We present sea ice temperature and salinity data from first-year ice (FYI) and second-year ice (SYI) relevant to the temporal development of sea ice permeability and brine drainage efficiency from the early growth phase in October 2019 to the onset of spring warming in May 2020. Our dataset was collected in the central Arctic Ocean during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) Expedition in 2019 to 2020. MOSAiC was an international transpolar drift expedition in which the German icebreaker RV Polarstern anchored into an ice floe to gain new insights into Arctic climate over a full annual cycle. In October 2019, RV Polarstern moored to an ice floe in the Siberian sector of the Arctic at 85 degrees north and 137 degrees east to begin the drift towards the North Pole and the Fram Strait via the Transpolar Drift Stream. The data presented here were collected during the first three legs of the expedition, so all the coring activities took place on the same floe. The end dates of legs 1, 2, and 3 were 13 December, 24 February, and 4 June, respectively. The dataset contributed to a baseline study entitled, Deciphering the properties of different Arctic ice types during the growth phase of the MOSAiC floes: Implications for future studies. The study highlights downward directed gas pathways in FYI and SYI by inferring sea ice permeability and potential brine release from several time series of temperature and salinity measurements. The physical properties presented in this paper lay the foundation for subsequent analyses on actual gas contents measured in the ice cores, as well as air-ice and ice-ocean gas fluxes. Sea ice cores were collected with a Kovacs Mark II 9 cm diameter corer. To measure ice temperatures, about 4.5 cm deep holes were drilled into the core (intervals varied by site and leg) . The temperatures were measured by a digital thermometer within minutes after the cores were retrieved. The ice cores were placed into pre-labelled plastic sleeves sealed at the bottom end. The ice cores were transported to RV Polarstern and stored in a -20 degrees Celsius freezer. Each of the cores was sub-sampled, melted at room temperature, and processed for salinity within one or two days. The practical salinity was estimated by measuring the electrical conductivity and temperature of the melted samples using a WTW Cond 3151 salinometer equipped with a Tetra-Con 325 four-electrode conductivity cell. The practical salinity represents the the salinity estimated from the electrical conductivity of the solution. The dataset also contains derived variables, including sea ice density, brine volume fraction, and the Rayleigh number.
    Language: English
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  • 26
    Publication Date: 2023-01-30
    Description: This dataset describes two 17 m long sediment cores taken from beneath two thermokarst lakes in the Yukechi Alas, Central Yakutia, Russia. The first core was taken from below an Alas thermokarst lake (YU-L7; 61.76397°N, 130.46442°E) and the second core below and Yedoma lake (YU-L15; 61.76086°N, 130.47466°E). The dataset presents biogeochemical and biomarker parameters of sediment cores YU-L7 and YU-L15. Biogeochemical analyses include total carbon (TC) content, total organic carbon (TOC) content, total nitrogen (TN) content. Biomarker parameters include the n-alkane concentration, average chain length (ACL), carbon preference index (CPI), brGDGT concentration, archaeol concentration and the isoGDGT-0 concentration. The n-alkanes were measured in the aliphatic fraction by gas chromatography-mass spectromety using a Trace GC Ultra coupled to a DSQ MS. The branched and isoprenoid glycerol dialkyl glycerol tetraethers, as well as the dialkyl glycerol diether lipid (archaeol) were measured in the NSO fraction using a Shimadzu LC-10AD high-performance liquid chromatograph coupled to a Finnigan TSQ 7000 mass spectrometer via an atmospheric pressure chemical ionization interface. The pH soil is the sediment pH which was assessed by adding 6.12 mL of 0.01 M CaCl~2~ to ~2.5 g dried sediment and measuring with a Multilab 540 (WTW) at 20°C.
    Language: English
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  • 27
    Publication Date: 2023-01-30
    Description: We present sea ice temperature and salinity data from first-year ice (FYI) and second-year ice (SYI) relevant to the temporal development of sea ice permeability and brine drainage efficiency from the early growth phase in October 2019 to the onset of spring warming in May 2020. Our dataset was collected in the central Arctic Ocean during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) Expedition in 2019 to 2020. MOSAiC was an international transpolar drift expedition in which the German icebreaker RV Polarstern anchored into an ice floe to gain new insights into Arctic climate over a full annual cycle. In October 2019, RV Polarstern moored to an ice floe in the Siberian sector of the Arctic at 85 degrees north and 137 degrees east to begin the drift towards the North Pole and the Fram Strait via the Transpolar Drift Stream. The data presented here were collected during the first three legs of the expedition, so all the coring activities took place on the same floe. The end dates of legs 1, 2, and 3 were 13 December, 24 February, and 4 June, respectively. The dataset contributed to a baseline study entitled, Deciphering the properties of different Arctic ice types during the growth phase of the MOSAiC floes: Implications for future studies. The study highlights downward directed gas pathways in FYI and SYI by inferring sea ice permeability and potential brine release from several time series of temperature and salinity measurements. The physical properties presented in this paper lay the foundation for subsequent analyses on actual gas contents measured in the ice cores, as well as air-ice and ice-ocean gas fluxes. Sea ice cores were collected with a Kovacs Mark II 9 cm diameter corer. To measure ice temperatures, about 4.5 cm deep holes were drilled into the core (intervals varied by site and leg) . The temperatures were measured by a digital thermometer within minutes after the cores were retrieved. The ice cores were placed into pre-labelled plastic sleeves sealed at the bottom end. The ice cores were transported to RV Polarstern and stored in a -20 degrees Celsius freezer. Each of the cores was sub-sampled, melted at room temperature, and processed for salinity within one or two days. The practical salinity was estimated by measuring the electrical conductivity and temperature of the melted samples using a WTW Cond 3151 salinometer equipped with a Tetra-Con 325 four-electrode conductivity cell. The practical salinity represents the the salinity estimated from the electrical conductivity of the solution. The dataset also contains derived variables, including sea ice density, brine volume fraction, and the Rayleigh number.
    Language: English
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  • 28
    Publication Date: 2023-01-30
    Description: Despite the importance of surface energy budgets (SEBs) for land-climate interactions in the Arctic, uncertainties in their prediction persist. In-situ observational data of SEB components - useful for research and model validation - are collected at relatively few sites across the terrestrial Arctic, and not all available datasets are readily interoperable. Furthermore, the terrestrial Arctic consists of a diversity of vegetation types, which are generally not well represented in land surface schemes of current Earth system models. Therefore, we here provide four datasets comprising: 1. Harmonized, standardized and aggregated in situ observations of SEB components at 64 vegetated and glaciated sites north of 60° latitude, in the time period 1994-2021 2. A description of all study sites and associated environmental conditions, including the vegetation types, which correspond to the classification of the Circumpolar Arctic Vegetation Map (CAVM, Raynolds et al. 2019). 3. Data generated in a literature synthesis from 358 study sites on vegetation or glacier (〉=60°N latitude) covered by 148 publications. 4. Metadata, including data contributor information and measurement heights of variables associated with Oehri et al. 2022.
    Language: English
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  • 29
    Publication Date: 2023-01-30
    Description: This dataset provides lithological data from ICDP core 5017-1-A, retrieved from the deep northern Dead Sea basin in 2010/11, for the last glacial-interglacial transition (ca. 17-11.5 ka BP). The microfacies of the Lisan Formation was investigated between ~101 and 88.5 m sediment depth below lake floor by continuous thin section microscopy, while additional macroscopic information is provided from core catchers, as well as from over- and underlying sediment sections. Thin sections were prepared following the standard procedure by Brauer and Casanova (2001) that was adjusted for salty sediments. Thin section analyses were performed on overlapping large-scale thin sections using a Zeiss Axiolab pol microscope at magnifications of 50-400x.
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  • 30
    Publication Date: 2023-01-30
    Language: English
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  • 31
    Publication Date: 2023-01-30
    Description: This dataset contains observations of water discharge rates and concentrations of dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC) from a polygonal tundra site in the Lena River Delta, Russia. This dataset also contains lateral carbon fluxes of DOC and DIC that were estimated from these observations. Additionally, this dataset contains vertical fluxes of carbon dioxide and methane from the same study site. All observations were recorded on Samoylov Island (N 72.377188, E 126.495144) in the summer of 2014. The abbreviations A1, A2 and B refer to three outflows on the island where the hydrological parameters were observed (A1: N 72.379991, E 126.480886; A2: N 72.380134, E 126.481433; B: N 72.381348, E 126.483482). All outflows were approximately 10 meters. More information can be found in https://doi.org/10.5194/bg-19-3863-2022.
    Language: English
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  • 32
    Publication Date: 2023-01-30
    Description: Despite the importance of surface energy budgets (SEBs) for land-climate interactions in the Arctic, uncertainties in their prediction persist. In situ observational data of SEB components - useful for research and model validation - are collected at relatively few sites across the terrestrial Arctic, and not all available datasets are readily interoperable. Furthermore, the terrestrial Arctic consists of a diversity of vegetation types, which are generally not well represented in land surface schemes of current Earth system models. This dataset describes the environmental conditions for 64 tundra and glacier sites (〉=60°N latitude) across the Arctic, for which in situ measurements of surface energy budget components were harmonized (see Oehri et al. 2022). These environmental conditions are (proxies of) potential drivers of SEB-components and could therefore be called SEB-drivers. The associated environmental conditions, include the vegetation types graminoid tundra, prostrate dwarf-shrub tundra, erect-shrub tundra, wetland complexes, barren complexes (≤ 40% horizontal plant cover), boreal peat bogs and glacier. These land surface types (apart from boreal peat bogs) correspond to the main classification units of the Circumpolar Arctic Vegetation Map (CAVM, Raynolds et al. 2019). For each site, additional climatic and biophysical variables are available, including cloud cover, snow cover duration, permafrost characteristics, climatic conditions and topographic conditions.
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  • 33
    Publication Date: 2023-02-01
    Description: This dataset contains over 30 marine Electrical Resistivity Tomography (ERT) profiles taken in September 2021 around Tuktoyaktuk Island (NWT / Beaufort Sea, Canada). The measurements were part of the “Mackenzie Delta Permafrost Field Campaign” (mCan2021) within the “Modular Observation solutions for Earth Systems” (MOSES) program. The collected profiles consist of numerous adjacent vertical soundings in a (quasi-symmetric) reciprocal Wenner-Schlumberger array, using a floating cable towed behind a boat. GPS records along the electrode streamer were taken, enabling the improvement of pre- processing by excluding measurements for which the cable was curved and electrode positions deviated too widely. The aim of the study was to determine the depth of the submarine permafrost. Cleaned data is provided in csv format.
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  • 34
    Publication Date: 2023-02-01
    Description: This collection contains permafrost related measurements in the Mackenzie Delta, NWT, Canada from the MOSES (Modular Observation Solutions for Earth Systems) field campaign in September 2021. The field campaign was focused on three subaquatic sites: a small thermokarst lake along the ITH just south of Trail Valley Creek, "Lake 3", an elongated lake with known methane occurence in the outer Mackenzie Delta, "Swiss Cheese Lake", and north and south of Tuktoyaktuk Island. At "Swiss Cheese Lake", we measured methane and CO2 concentrations in surface water and in the air above the lake, lake bed temperatures and detailed bathymetry. At "Lake 3" we measured active layer thickness on the lake banks, lake bed temperatures, and detailed bathymetry, as well as an ERT survey to estimate the talik depth below the lake. North and south of Tuktoyaktuk Island, we measured active layer thickness and sea bed temperatures and did an extensive ERT survey to obtain the depth of the subsea permafrost table. An additional passive seismic survey was carried out and the data is available at https://doi.org/10.5880/GIPP.202199.1.
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  • 35
    Publication Date: 2023-02-01
    Description: This dataset contains seven Electrical Resistivity Tomography (ERT) profiles taken in September 2021 at “Lake 3”, a thermokarst lake near the Inuvik-Tuktoyaktuk-Highway (ITH), about 50 km north of Inuvik (NWT, Canada). The measurements were part of the “Mackenzie Delta Permafrost Field Campaign” (mCan2021) within the “Modular Observation solutions for Earth Systems” (MOSES) program. The collected profiles consist of numerous adjacent vertical soundings in a (quasi-symmetric) reciprocal Wenner-Schlumberger array. In addition to surveys on the lake, using a floating cable towed behind a boat, two “amphibian” profiles were taken. Starting as purely terrestrial surveys using metal spike electrodes, the cable was then moved towards the lake with some of the electrodes floating on the water surface, and some still on land. The aim of the study was to determine permafrost properties on the land, to detect a possible talik beneath the lake and to especially be able to infer the transition between the two below the shoreline.
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  • 36
    Publication Date: 2024-01-19
    Description: Presented are analytical data from lacustrine sediment cores, retrieved from Lake Nam Co (Tibetan Plateau). The sediment core is a composite of one gravity core, taken with a Rumohr-Meischner gravity corer (63 mm diameter) and a piston core, retrieved using an uwitec piston coring system (http://www.uwitec.at; 90 mm diameter). The composite core labelled 〈NC 08/01〉 comprises a total length of 10.378 m. The cores were obtained at N 30.737417, E 090.790333 at a water depth of 93 m on 2008-09-15. The purpose of obtaining this sediment core was to establish a high-resolution record of climate (monsoonal) and environmental change using multiple proxy data. The dataset comprises analytical data based on sedimentological, inorganic geochemical, mineralogical and isotope-geochemical methods. Specifically: sediment water content & density; magnetic susceptibility; particel size data; quantitative inorganic geochemical data (ICP-OES aqua regia and HCL digestions); semi-quantitative XRF elemental data; carbon, nitrogen, sulfur contents; qualitative mineralogical data; bulk sediment stable carbon and oxygen isotope data.
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  • 37
    Publication Date: 2024-01-19
    Description: This data set is part of a larger data harmonization effort to make lake sediment core data machine readable and comparable. Here we standardized X-ray fluorescence line scanning (XRF)-based element data of sediment core EN18208, retrieved in 2018 from Lake Ilirney (Chukotka, Russia) at 10.76 m water depth. The glacial lake Ilirney is situated in the forest tundra mountain area and has one outflow, one main inflow and several smaller inflows. It lies at an elevation of ca. 428 m a.s.l. with a surface area of ca. 30 km2 and a maximum lake water depth of estimated 44 m. The 10.76 m sediment core was retrieved by a UWITEC piston corer during the RU-Land_2018_Chukotka expedition of the Alfred Wegener Institute Helmholtz Centre for Polar and Marine Research (AWI, Germany, Potsdam) in cooperation with the North Eastern Federal State University (NEFU, Russia, Yakutsk). The downcore elemental composition was measured using an AVAATECH x-ray fluorescence core scanner at Bundesanstalt für Geowissenschaften und Rohstoffe (BGR) in Berlin, Spandau.
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  • 38
    Publication Date: 2024-01-19
    Description: This data set is part of a larger data harmonization effort to make lake sediment core data machine readable and comparable. Here we standardized radiocarbon and OSL age data of sediment core EN18208, retrieved in 2018 from Lake Ilirney (Chukotka, Russia) at 10.76 m water depth. The glacial lake Ilirney is situated in the forest tundra mountain area and has one outflow, one main inflow and several smaller inflows. It lies at an elevation of ca. 428 m a.s.l. with a surface area of ca. 30 km2 and a maximum lake water depth of estimated 44 m. The 10.76 m sediment core was retrieved by a UWITEC piston corer during the RU-Land_2018_Chukotka expedition of the Alfred Wegener Institute Helmholtz Centre for Polar and Marine Research (AWI, Germany, Potsdam) in cooperation with the North Eastern Federal State University (NEFU, Russia, Yakutsk). Radiocarbon data have been analysed from bulk sediment samples in Bremerhaven at the MICADAS laboratory. Optically stimulated luminescence (OSL) dating was performed at the Royal Holloway Luminescence Laboratory using a Risø TL/OSL-DA-15 automated dating system.
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  • 39
    Publication Date: 2024-01-19
    Description: A 25-cm long predominantly aragonite stalagmite was collected November 2, 2005 from Dharamjali Cave (29.5°N, 80.2°E) in the central Himalayas. This dataset contains stable isotope, trace element, XRF, U/Th dating, and dripwater data. The age model spans 4.2 to 2.3 ka BP, and the dataset records seasonal shifts in hydroclimate from 4.2 to 3.1 ka BP. Using the DHAR-1A half of the speleothem, 750 samples were milled at 100–300 µm resolution for stable isotope analysis (δ18O and δ13C) and analyzed at GFZ Potsdam. Further high-resolution stable isotope analysis at the University of Cambridge included 876 samples from the bottom 4 cm of the mirroring slab DHAR-1B, covering c. 4.2–3.6 ka BP. The δ44/40Ca measurements were made on 60 aragonite samples of aragonite and 1 calcite sample milled between 4.2 and 2.8 ka BP. The elemental composition of DHAR-1B was determined first with an Avaatech XRF scanner at the University of Cambridge, and later using laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) at the University of Waikato. U-series dating was performed at Caltech on 22 samples. Twelve U-series ages (between 2.55 and 4.14 ka BP) were used to construct the age models, using ensembles of 2000 Monte Carlo simulations for each proxy using the MATLAB-based COPRA script (Breitenbach et al., 2012, https://doi.org/10.5194/cp-8-1765-2012).
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  • 40
    Publication Date: 2024-01-19
    Description: This data set is part of a larger data harmonization effort to make lake sediment core data machine readable and comparable. Here we standardized grain size element data of sediment core EN18208, retrieved in 2018 from Lake Ilirney (Chukotka, Russia) at 10.76 m water depth. The glacial lake Ilirney is situated in the forest tundra mountain area and has one outflow, one main inflow and several smaller inflows. It lies at an elevation of ca. 428 m a.s.l. with a surface area of ca. 30 km2 and a maximum lake water depth of estimated 44 m. The 10.76 m sediment core was retrieved by a UWITEC piston corer during the RU-Land_2018_Chukotka expedition of the Alfred Wegener Institute Helmholtz Centre for Polar and Marine Research (AWI, Germany, Potsdam) in cooperation with the North Eastern Federal State University (NEFU, Russia, Yakutsk). Grain-size was measured using a Malvern Mastersizer 3000 laser diffraction particle analyser.
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  • 41
    Publication Date: 2024-01-19
    Description: This data set is part of a larger data harmonization effort to make lake sediment core data machine readable and comparable. Here we standardized mineral data of sediment core EN18208, retrieved in 2018 from Lake Ilirney (Chukotka, Russia) at 10.76 m water depth. The glacial lake Ilirney is situated in the forest tundra mountain area and has one outflow, one main inflow and several smaller inflows. It lies at an elevation of ca. 428 m a.s.l. with a surface area of ca. 30 km2 and a maximum lake water depth of estimated 44 m. The 10.76 m sediment core was retrieved by a UWITEC piston corer during the RU-Land_2018_Chukotka expedition of the Alfred Wegener Institute Helmholtz Centre for Polar and Marine Research (AWI, Germany, Potsdam) in cooperation with the North Eastern Federal State University (NEFU, Russia, Yakutsk). Bulk mineralogy was analysed by (x-ray diffractometry (XRD) using a (PHILIPS, Netherlands) PW1820 goniometer.
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  • 42
    Publication Date: 2024-01-19
    Description: This data set is part of a larger data harmonization effort to make lake sediment core data machine readable and comparable. Here we standardized radiocarbon and OSL age data of sediment core EN18208, retrieved in 2018 from Lake Ilirney (Chukotka, Russia) at 10.76 m water depth. The glacial lake Ilirney is situated in the forest tundra mountain area and has one outflow, one main inflow and several smaller inflows. It lies at an elevation of ca. 428 m a.s.l. with a surface area of ca. 30 km2 and a maximum lake water depth of estimated 44 m. The 10.76 m sediment core was retrieved by a UWITEC piston corer during the RU-Land_2018_Chukotka expedition of the Alfred Wegener Institute Helmholtz Centre for Polar and Marine Research (AWI, Germany, Potsdam) in cooperation with the North Eastern Federal State University (NEFU, Russia, Yakutsk). Water content and organic matter was analysed at AWI Potsdam. Dried and milled samples were analysed using a Vario EL III carbon-nitrogen-sulphur analyser. Organic carbon content was determined using a Vario MAX C analyser.
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  • 43
    Publication Date: 2023-09-18
    Description: Surface air temperature measurements obtained from different sensors are used to construct a unique time series with one minute time-interval. Apart from differences in design and environmental exposition, periods of missing data also exist in the data series of each sensor. A primary data set was selected in terms of quality and temporal extension. A combination of two different techniques is applied to complete this data set: one is based on the autocorrelation of the series and the other on measurements taken from other sensors. The resulting values constitute a complete series of surface air temperature at AGGO.
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  • 44
  • 45
    Publication Date: 2024-01-24
    Description: This dataset contain stable isotope values for water samples collected ~weekly from the Rio Bermejo at the Lavalle bridge (-25.6513, -60.1277) from March 2016 to February 2018. Water samples were filtered to 0.2 micron using a custom filtration device. We measured d2H and d18O on a Picarro L-2140i Cavity Ring-Down Spectrometer at the GFZ Potsdam. Measurements were made in duplicate, normalized to the Vienna Standard Mean Ocean Water (VSMOW), and analytical uncertainty is reported as one standard deviation from the mean. River discharge was measured at the El Colorado gauging station, which is ~100 km down slope from the sampling location.
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  • 46
    Publication Date: 2024-01-24
    Description: This dataset provides the geochemistry data for the Holocene sediment sequence retrieved from Lake Uddelermeer (The Netherlands) in 2012. Additionally, alkane concentrations for a set of modern leaf samples are provided. Concentrations of fossil alkanes, GDGTs as well as elemental (C, N, S, H) and compound-specific delta Deuterium measurements are presented against both depth (cm) and age (cal yr. BP). A total of 59 samples were analysed. Modern leaf alkane concentrations are presented as concentrations, 10 samples were analysed. The geochemical data provides information about regional vegetation change as well as changes in effective precipitation. It was produced to inform on the age and duration of major environmental transitions during the middle and late Holocene. Cores were retrieved from the lake using a 3-m long handheld piston corer deployed from a floating coring platform during field work in April and May 2012. Samples were obtained from splits of the core and processed in the laboratory of the University of Amsterdam (the Netherlands) using standard protocols (CNHS, alkane concentrations), the laboratory of Utrecht University (the Netherlands; GDGT concentrations) and at GFZ Potsdam (Germany; delta Deuterium). Name of the Campaign: UDD Event Label: UDD-E Method: Uwitec piston corer Latitude: 52.24652778 Longitude: 5.76097222 Elevation: 24m asl Date/Time of event: 2012-05-01T14:00:00 Further information about event: Lake sediment sequence retrieved using a 60 mm piston corer deployed from a floating platform.
    Language: English
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  • 47
    Publication Date: 2024-01-24
    Description: Water samples were filtered to 0.2 micron prior to measurement. Samples for cation analysis were acidified in the field to pH 〈 2 using 6N HNO3. Cation concentrations were measured with a Varian 720 inductively coupled plasma optical emission spectrometer (ICP-OES) at the GFZ Helmholtz Laboratory for the Geochemistry of the Earth Surface (HELGES), using SLRS-5 (Saint-Laurent River Surface, National Research Council - Conseil National de Recherches Canada) and USGS M212 and USGS T187 as external standards. We corrected for instrument drift by measuring an internal standard (GFZ-RW1) every 10 samples and we determined measurement uncertainty using calibration curve uncertainty. Anion concentrations were measured with a Dionex ICS1100 Ion Chromatograph, using USGS standards M206 and M212 as external standards for quality control, with uncertainty determined from triplicate analysis. We corrected cation concentrations for cyclic salt inputs following Bickle et al. (2005, doi:10.1016/j.gca.2004.11.019).
    Language: English
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  • 48
    Publication Date: 2024-04-11
    Description: This dataset reports measurements from a laboratory incubation of soils sourced from a boreal peatland and surrounding habitats (Siikaneva Bog, Finland). In August 2021, soil cores were collected from three habitat zones: a well-drained upland forest, an intermediate margin ecotone, and a Sphagnum moss bog. The cores from each habitat were taken from surface to approximately 50cm below surface using an Eijelkamp peat corer and subdivided by soil horizon. The samples were then incubated anaerobically for 140 days in three temperature treatment groups (0, 4, 20°C). Subsamples of the incubations headspace (250 µL) were measured on a gas chromatograph (7890A, Agilent Technologies, USA) with flame ionization detection (FID) for CO2 and CH4 concentrations. The rate of respiration from the samples were calculated per gram carbon and per gram soil as described in the method of Robertson., et al. (1999) and reported here, along with other relevant parameters.
    Language: English
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  • 49
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    The Journal of Chemical Physics 91 (1989), S. 4455-4461 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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.
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  • 50
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    The Journal of Chemical Physics 91 (1989), S. 4477-4484 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 51
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    The Journal of Chemical Physics 91 (1989), S. 4499-4503 
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    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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.
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  • 52
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    The Journal of Chemical Physics 91 (1989), S. 4582-4586 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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.
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  • 53
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    The Journal of Chemical Physics 91 (1989), S. 4597-4602 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 54
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    The Journal of Chemical Physics 91 (1989), S. 4636-4642 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 55
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    The Journal of Chemical Physics 91 (1989), S. 4643-4650 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 56
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    The Journal of Chemical Physics 91 (1989), S. 4714-4727 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 57
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    The Journal of Chemical Physics 91 (1989), S. 4738-4744 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 58
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    The Journal of Chemical Physics 91 (1989), S. 4785-4792 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 59
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    The Journal of Chemical Physics 91 (1989), S. 4909-4911 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 60
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    The Journal of Chemical Physics 91 (1989), S. 4920-4925 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 61
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    The Journal of Chemical Physics 91 (1989), S. 4942-4948 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 62
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    The Journal of Chemical Physics 91 (1989), S. 4338-4345 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 63
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    The Journal of Chemical Physics 91 (1989), S. 4265-4272 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 64
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    The Journal of Chemical Physics 91 (1989), S. 4299-4306 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 65
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    The Journal of Chemical Physics 91 (1989), S. 4330-4337 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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    The Journal of Chemical Physics 91 (1989), S. 4360-4368 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 67
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    The Journal of Chemical Physics 91 (1989), S. 4387-4400 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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    The Journal of Chemical Physics 91 (1989), S. 4418-4419 
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    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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    The Journal of Chemical Physics 91 (1989), S. 4425-4426 
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    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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    The Journal of Chemical Physics 91 (1989), S. 3525-3531 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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    The Journal of Chemical Physics 91 (1989), S. 3571-3576 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 72
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    Notes: 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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  • 73
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    The Journal of Chemical Physics 91 (1989), S. 3689-3699 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 74
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    The Journal of Chemical Physics 91 (1989), S. 3721-3723 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 75
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    The Journal of Chemical Physics 91 (1989), S. 5154-5159 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 76
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    The Journal of Chemical Physics 91 (1989), S. 5139-5153 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 77
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    The Journal of Chemical Physics 91 (1989), S. 5164-5169 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 78
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    The Journal of Chemical Physics 91 (1989), S. 5160-5163 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 79
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    The Journal of Chemical Physics 91 (1989), S. 3792-3793 
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  • 80
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    The Journal of Chemical Physics 91 (1989), S. 2776-2778 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 81
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    The Journal of Chemical Physics 91 (1989), S. 3596-3602 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 82
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    The Journal of Chemical Physics 91 (1989), S. 5185-5200 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 83
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    The Journal of Chemical Physics 91 (1989), S. 5201-5207 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 84
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    The Journal of Chemical Physics 91 (1989), S. 3647-3661 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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    The Journal of Chemical Physics 91 (1989), S. 3700-3706 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 86
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    The Journal of Chemical Physics 91 (1989), S. 3724-3728 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 87
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    The Journal of Chemical Physics 91 (1989), S. 3744-3761 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 88
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    The Journal of Chemical Physics 91 (1989), S. 2771-2775 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 89
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    The Journal of Chemical Physics 91 (1989), S. 2808-2813 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 90
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    The Journal of Chemical Physics 91 (1989), S. 2840-2847 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 91
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    The Journal of Chemical Physics 91 (1989), S. 2892-2897 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 92
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    The Journal of Chemical Physics 91 (1989), S. 2912-2921 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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  • 93
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    The Journal of Chemical Physics 91 (1989), S. 2102-2107 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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    The Journal of Chemical Physics 91 (1989), S. 2971-2979 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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    The Journal of Chemical Physics 91 (1989), S. 3002-3011 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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    The Journal of Chemical Physics 91 (1989), S. 3045-3055 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: 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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    The Journal of Chemical Physics 91 (1989), S. 5313-5315 
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    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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.
    Type of Medium: Electronic Resource
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  • 98
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5324-5328 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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.
    Type of Medium: Electronic Resource
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  • 99
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5329-5334 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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.
    Type of Medium: Electronic Resource
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  • 100
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5316-5323 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 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.
    Type of Medium: Electronic Resource
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