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  • American Physical Society  (663,490)
  • Molecular Diversity Preservation International  (495,622)
  • American Institute of Physics (AIP)  (241,959)
Collection
Publisher
Years
  • 1
    Journal cover
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    American Crystallographic Association (ACA) | American Institute of Physics (AIP)
    Online: 1(1).2014 –
    Publisher: American Crystallographic Association (ACA) , American Institute of Physics (AIP)
    Electronic ISSN: 2329-7778
    Topics: Physics
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  • 2
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    American Institute of Physics (AIP)
    Online: 1(1).1989 – 5(12).1993
    Online: 1(1).1989 – 5(12).1993
    Publisher: American Institute of Physics (AIP)
    Print ISSN: 0899-8221
    Topics: Physics
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  • 3
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    American Institute of Physics (AIP)
    Online: 1.1958 –
    Formerly as: Physics of Fluids A: Fluid Dynamics ; Physics of Fluids B: Plasma Physics  (1989–1993)
    Publisher: American Institute of Physics (AIP)
    Print ISSN: 0031-9171 , 1070-6631
    Electronic ISSN: 1089-7666
    Topics: Physics
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  • 4
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    American Institute of Physics (AIP)
    Online: 1.1930 –
    Print: 28.1957 – 41.1970 (Location: A18, ---)
    Formerly as: Review of Scientific Instruments with Physics News and Views  (1933–1938)
    Publisher: American Institute of Physics (AIP)
    Print ISSN: 0034-6748
    Electronic ISSN: 1089-7623
    Topics: Electrical Engineering, Measurement and Control Technology , Physics
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  • 5
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    American Institute of Physics (AIP)
    Online: 23.1997 –
    Publisher: American Institute of Physics (AIP)
    Print ISSN: 1063-777X
    Electronic ISSN: 1090-6517
    Topics: Physics
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  • 6
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    American Institute of Physics (AIP) | früher: Elsevier
    Online: 1(1).2016 –
    Publisher: American Institute of Physics (AIP) , früher: Elsevier
    Print ISSN: 2468-2047
    Electronic ISSN: 2468-080X
    Topics: Physics
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  • 7
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    American Institute of Physics (AIP)
    Online: 1.1933 –
    Publisher: American Institute of Physics (AIP)
    Print ISSN: 0021-9606
    Electronic ISSN: 1089-7690
    Topics: Chemistry and Pharmacology , Physics
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  • 8
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    Society of Rheology (SoR) | American Institute of Physics (AIP)
    Online: 1(1).1929 –
    Formerly as: Transactions of the Society of Rheology  (1957–1977)
    Publisher: Society of Rheology (SoR) , American Institute of Physics (AIP)
    Print ISSN: 0038-0032 , 0097-0360 , 0148-6055
    Electronic ISSN: 1520-8516
    Topics: Physics
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  • 9
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    American Physical Society
    Online: 1995 –
    Publisher: American Physical Society
    Topics: Physics
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  • 10
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    American Institute of Physics (AIP)
    Online: 1.1931 –
    Formerly as: Physics  (1931–1936)
    Publisher: American Institute of Physics (AIP)
    Print ISSN: 0021-8979
    Electronic ISSN: 1089-7550
    Topics: Physics
    Acronym: JAP
    Abbreviation: J Appl Phys
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  • 11
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    Laser Institute of America (LIA) | American Institute of Physics (AIP)
    Online: 1(1).1988 –
    Publisher: Laser Institute of America (LIA) , American Institute of Physics (AIP)
    Print ISSN: 1042-346X
    Electronic ISSN: 1938-1387
    Topics: Physics
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  • 12
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    American Institute of Physics (AIP)
    Online: 1.1960 –
    Publisher: American Institute of Physics (AIP)
    Print ISSN: 0022-2488
    Electronic ISSN: 1089-7658
    Topics: Mathematics , Physics
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  • 13
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    American Physical Society
    Online: 1.1998 –
    Formerly as: Physical Review Focus  (1998–2011)
    Publisher: American Physical Society
    Electronic ISSN: 1943-2879
    Topics: Physics
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  • 14
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    American Institute of Physics (AIP)
    Online: 1(1).1989 – 5(12).1993
    Online: 1(1).1989 – 5(12).1993
    Publisher: American Institute of Physics (AIP)
    Print ISSN: 0899-8213
    Topics: Physics
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  • 15
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    American Physical Society
    Online: 1(1).1964 – 4(1).1968
    Publisher: American Physical Society
    Topics: Physics
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  • 16
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    American Physical Society
    Online: 1.2017 –
    Publisher: American Physical Society
    Electronic ISSN: 2475-9953
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 17
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    American Physical Society
    Online: 1(1).2019 –
    Publisher: American Physical Society
    Electronic ISSN: 2643-1564
    Topics: Physics
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  • 18
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    American Institute of Physics (AIP)
    Online: 1.1994 –
    Publisher: American Institute of Physics (AIP)
    Print ISSN: 1070-664X
    Electronic ISSN: 1089-7674
    Topics: Physics
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  • 19
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    American Institute of Physics (AIP)
    Online: 1.2009 –
    Publisher: American Institute of Physics (AIP)
    Electronic ISSN: 1941-7012
    Topics: Energy, Environment Protection, Nuclear Power Engineering
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  • 20
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    American Institute of Physics (AIP)
    Online: 52.1999 –
    Print: 39(7).1986 – 45.1992 (Location: A17, Kompaktmagazin, 58/6-7)
    Print: 44.1991 – 63.2010 (Location: A43, Archiv)
    Print: 46.1993 – 71.2018 (Location: A17, Kompaktmagazin, 58/6-7)
    Publisher: American Institute of Physics (AIP)
    Print ISSN: 0031-9228
    Electronic ISSN: 1945-0699
    Topics: Physics
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  • 21
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    American Institute of Physics (AIP)
    Online: 1.1969 – 34.2002
    Publisher: American Institute of Physics (AIP)
    Print ISSN: 0002-7537
    Topics: Physics
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  • 22
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    American Institute of Physics (AIP) | IEEE Computer Society | Institute of Electrical and Electronics Engineers (IEEE)
    Online: 1.1999 –
    Publisher: American Institute of Physics (AIP) , IEEE Computer Society , Institute of Electrical and Electronics Engineers (IEEE)
    Print ISSN: 1521-9615
    Electronic ISSN: 1558-366X
    Topics: Computer Science , Natural Sciences in General , Technology
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  • 23
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    American Physical Society
    Online: 1993 –
    Publisher: American Physical Society
    Print ISSN: 0003-0503
    Topics: Physics
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  • 24
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    American Institute of Physics (AIP)
    Online: 36.2004 –
    Publisher: American Institute of Physics (AIP)
    Print ISSN: 0148-5857
    Topics: Physics
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  • 25
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    American Institute of Physics (AIP)
    Online: 1.1991 –
    Publisher: American Institute of Physics (AIP)
    Print ISSN: 1054-1500
    Electronic ISSN: 1089-7682
    Topics: Physics
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  • 26
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    American Physical Society
    Online: 4(5).1995 –
    Publisher: American Physical Society
    Print ISSN: 1058-8132
    Topics: Physics
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  • 27
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    American Institute of Physics (AIP) | American Crystallographic Association (ACA)
    Online: 1.2011 –
    Publisher: American Institute of Physics (AIP) , American Crystallographic Association (ACA)
    Electronic ISSN: 2158-3226
    Topics: Physics
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  • 28
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    American Institute of Physics (AIP)
    Online: 1(1).1970 –
    Publisher: American Institute of Physics (AIP)
    Print ISSN: 0094-243X
    Electronic ISSN: 1551-7616
    Topics: Physics
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  • 29
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    American Institute of Physics (AIP)
    Online: 1.1962 – 123.2023
    Publisher: American Institute of Physics (AIP)
    Print ISSN: 0003-6951
    Electronic ISSN: 1077-3118
    Topics: Physics
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  • 30
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    American Institute of Physics (AIP)
    Online: 1.1975 – 29.2003
    Formerly as: Soviet Astronomy / Letters. A translation of the Astronomical journal of the Soviet Academy of Sciences of the USSR  (1975–1992)
    Publisher: American Institute of Physics (AIP)
    Print ISSN: 0360-0327 , 1063-7737
    Topics: Physics
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  • 31
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    American Institute of Physics (AIP)
    Online: 1.2013 –
    Publisher: American Institute of Physics (AIP)
    Electronic ISSN: 2166-532X
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Keywords: Werkstoffkunde
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  • 32
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    American Institute of Physics (AIP)
    Online: 1(1).2016 –
    Publisher: American Institute of Physics (AIP)
    Electronic ISSN: 2378-0967
    Topics: Physics
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  • 33
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    American Institute of Physics (AIP)
    Online: 1(1).2014 –
    Publisher: American Institute of Physics (AIP)
    Electronic ISSN: 1931-9401
    Topics: Physics
    Keywords: Allgemeine Physik
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  • 34
    Publication Date: 2020-10-16
    Description: We propose a version of the pure temporal epidemic type aftershock sequences (ETAS) model: the ETAS model with correlated magnitudes. As for the standard case, we assume the Gutenberg-Richter law to be the probability density for the magnitudes of the background events. Instead, the magnitude of the triggered shocks is assumed to be probabilistically dependent on that of the relative mother events. This probabilistic dependence is motivated by some recent works in the literature and by the results of a statistical analysis made on some seismic catalogs [Spassiani and Sebastiani, J. Geophys. Res. 121, 903 (2016)10.1002/2015JB012398]. On the basis of the experimental evidences obtained in the latter paper for the real catalogs, we theoretically derive the probability density function for the magnitudes of the triggered shocks proposed in Spassiani and Sebastiani and there used for the analysis of two simulated catalogs. To this aim, we impose a fundamental condition: averaging over all the magnitudes of the mother events, we must obtain again the Gutenberg-Richter law. This ensures the validity of this law at any event's generation when ignoring past seismicity. The ETAS model with correlated magnitudes is then theoretically analyzed here. In particular, we use the tool of the probability generating function and the Palm theory, in order to derive an approximation of the probability of zero events in a small time interval and to interpret the results in terms of the interevent time between consecutive shocks, the latter being a very useful random variable in the assessment of seismic hazard.
    Description: Published
    Description: 042134
    Description: 6T. Studi di pericolosità sismica e da maremoto
    Description: JCR Journal
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 35
    Publication Date: 2021-06-30
    Description: In the present work, the Differential SAR Interferometry (DInSAR) technique has been applied to study the surface movements affecting the sedimentary basin of Cassino municipality. Two datasets of SAR images, provided by ERS 1-2 and Envisat missions, have been acquired from 1992 to 2010. Such datasets have been processed independently each other and with different techniques nevertheless providing compatible results. DInSAR data show a subsidence rate mostly located in the northeast side of the city, with a subsidence rate decreasing from about 5–6 mm/yr in the period 1992–2000 to about 1–2 mm/yr between 2004 and 2010, highlighting a progressive reduction of the phenomenon. Based on interferometric results and geological/geotechnical observations, the explanation of the detected movements allows to confirm the anthropogenic (surface effect due to building construction) and geological causes (thickness and characteristics of the compressible stratum)
    Description: Published
    Description: 9676-9690
    Description: 6A. Monitoraggio ambientale, sicurezza e territorio
    Description: JCR Journal
    Description: open
    Keywords: Differential SAR Interferometry; SBAS; IPTA; Cassino plain; subsidence ; 04. Solid Earth::04.01. Earth Interior::04.01.02. Geological and geophysical evidences of deep processes
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 36
    Publication Date: 2017-04-04
    Description: We perform an analysis on the dissipative Olami-Feder-Christensen model on a small world topology considering avalanche size differences. We show that when criticality appears, the probability density functions (PDFs) for the avalanche size differences at different times have fat tails with a q-Gaussian shape. This behavior does not depend on the time interval adopted and is found also when considering energy differences between real earthquakes. Such a result can be analytically understood if the sizes (released energies) of the avalanches (earthquakes) have no correlations. Our findings support the hypothesis that a self-organized criticality mechanism with long-range interactions is at the origin of seismic events and indicate that it is not possible to predict the magnitude of the next earthquake knowing those of the previous ones.
    Description: Published
    Description: 2.3. TTC - Laboratori di chimica e fisica delle rocce
    Description: JCR Journal
    Description: reserved
    Keywords: SOC, earthquakes interaction ; 05. General::05.01. Computational geophysics::05.01.04. Statistical analysis
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 37
    Publication Date: 2017-04-04
    Description: Italy has a strong geothermal potential for power generation, although, at present, the only two geothermal fields being exploited are Larderello-Travale/Radicondoli and Mt. Amiata in the Tyrrhenian pre-Apennine volcanic district of Southern Tuscany. A new target for geothermal exploration and exploitation in Italy is represented by the Southern Tyrrhenian submarine volcanic district, a geologically young basin (Upper Pliocene-Pleistocene) characterised by tectonic extension where many seamounts have developed. Heat-flow data from that area show significant anomalies comparable to those of onshore geothermal fields. Fractured basaltic rocks facilitate seawater infiltration and circulation of hot water chemically altered by rock/water interactions, as shown by the widespread presence of hydrothermal deposits. The persistence of active hydrothermal activity is consistently shown by many different sources of evidence, including: heat-flow data, gravity and magnetic anomalies, widespread presence of hydrothermal-derived gases (CO2, CO, CH4), 3He/4He isotopic ratios, as well as broadband OBS/H seismological information, which demonstrates persistence of volcano-tectonic events and High Frequency Tremor (HFT). The Marsili and Tyrrhenian seamounts are thus an important—and likely long-lasting-renewable energy resource. This raises the possibility of future development of the world’s first offshore geothermal power plant.
    Description: Published
    Description: 4068-4086
    Description: 3A. Ambiente Marino
    Description: JCR Journal
    Description: open
    Keywords: Marsili seamount ; hydrothermal circulation ; geothermal resource ; 04. Solid Earth::04.04. Geology::04.04.04. Marine geology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 38
    Publication Date: 2019-03-28
    Description: The understanding of the dynamical properties of skyrmion is a fundamental aspect for the realization of a competitive skyrmion based technology beyond CMOS. Most of the theoretical approaches are based on the approximation of a rigid skyrmion. However, thermal fluctuations can drive a continuous change of the skyrmion size via the excitation of thermal modes. Here, by taking advantage of the Hilbert-Huang transform, we demonstrate that at least two thermal modes can be excited which are non-stationary in time. In addition, one limit of the rigid skyrmion approximation is that this hypothesis does not allow for correctly describing the recent experimental evidence of skyrmion Hall angle dependence on the amplitude of the driving force, which is proportional to the injected current. In this work, we show that, in an ideal sample, the combined effect of field-like and damping-like torques on a breathing skyrmion can indeed give rise to such a current dependent skyrmion Hall angle. While here we design and control the breathing mode of the skyrmion, our results can be linked to the experiments by considering that the thermal fluctuations and/or disorder can excite the breathing mode. We also propose an experiment to validate our findings.
    Description: Published
    Description: 224418
    Description: 1A. Geomagnetismo e Paleomagnetismo
    Description: 2IT. Laboratori analitici e sperimentali
    Description: JCR Journal
    Keywords: Physics - Mesoscopic Systems and Quantum Hall Effect ; Physics - Mesoscopic Systems and Quantum Hall Effect
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 39
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    American Physical Society
    In:  EPIC3Physical Review E, American Physical Society, 90, pp. 022711-1, ISSN: 1539-3755
    Publication Date: 2014-11-04
    Description: The fascinating ability of algae, insects, and fishes to survive at temperatures below normal freezing is realized by antifreeze proteins (AFPs). These are surface-active molecules and interact with the diffusive water-ice interface thus preventing complete solidification. We propose a dynamical mechanism on how these proteins inhibit the freezing of water. We apply a Ginzburg-Landau-type approach to describe the phase separation in the two-component system (ice, AFP). The free-energy density involves two fields: one for the ice phase with a low AFP concentration and one for liquid water with a high AFP concentration. The time evolution of the ice reveals microstructures resulting from phase separation in the presence of AFPs. We observed a faster clustering of pre-ice structure connected to a locking of grain size by the action of AFP, which is an essentially dynamical process. The adsorption of additional water molecules is inhibited and the further growth of ice grains stopped. The interfacial energy between ice and water is lowered allowing the AFPs to form smaller critical ice nuclei. Similar to a hysteresis in magnetic materials we observe a thermodynamic hysteresis leading to a nonlinear density dependence of the freezing point depression in agreement with the experiments.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
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  • 40
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    American Physical Society
    In:  EPIC3Physical Review E, American Physical Society, 88(6), ISSN: 1539-3755
    Publication Date: 2018-02-16
    Description: In this study we model population dynamics in a three-species food web with heterogeneous resources and intraguild predation by using a nonspatial Lotka-Volterra system with a density-dependent interaction of resource items. The model consists of two predators with an intraguild predation (IGP) relation competing for a common resource. The resource is subdivided into subpopulations of different quality that are distinguished by grazing rates of the two predators, contact rates between subpopulations and mortality rates. The proposed system describes an exchange of traits between species from distinct subpopulations by using a species interaction term. In particular, we examine the percentage of stable coexistence solutions versus resource carrying capacity and contact rates between distinct resource pools. We also present a numerical comparison of the percentage of stable food webs found for different numbers of subpopulations. While at high enrichment no stable coexistence was found in the IGP system with a single resource, our model predicts a stable coexistence of two IGP-related predators and resources at high and intermediate enrichment already at a low contact rate between subpopulations.
    Repository Name: EPIC Alfred Wegener Institut
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  • 41
    Publication Date: 2022-05-25
    Description: © 2009 The Authors. This article is distributed under the terms of the Creative Commons Attribution (3.0) License. The definitive version was published in Sensors 9 (2009): 404-429, doi:10.3390/s90100404.
    Description: An instrument has been built to carry out continuous in-situ measurement of small differences in water pressure, conductivity and temperature, in natural surface water and groundwater systems. A low-cost data telemetry system provides data on shore in real time if desired. The immediate purpose of measurements by this device is to continuously infer fluxes of water across the sediment-water interface in a complex estuarine system; however, direct application to assessment of sediment-water fluxes in rivers, lakes, and other systems is also possible. Key objectives of the design include both low cost, and accuracy of the order of ±0.5 mm H2O in measured head difference between the instrument’s two pressure ports. These objectives have been met, although a revision to the design of one component was found to be necessary. Deployments of up to nine months, and wireless range in excess of 300 m have been demonstrated.
    Keywords: Pressure sensor ; Wireless ; Hydrology ; Data logger ; Oceanographic instrumentation
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 42
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    American Physical Society
    Publication Date: 2022-05-25
    Description: © The Author(s), 2015. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Physical Review E Statistical, Nonlinear, and Soft Matter Physics 92 (2015): 052128, doi: 10.1103/PhysRevE.92.052128.
    Description: Studies over the past decade have reported power-law distributions for the areas of terrestrial lakes and Arctic melt ponds, as well as fractal relationships between their areas and coastlines. Here we report similar fractal structure of ponds in a tidal flat, thereby extending the spatial and temporal scales on which such phenomena have been observed in geophysical systems. Images taken during low tide of a tidal flat in Damariscotta, Maine, reveal a well-resolved power-law distribution of pond sizes over three orders of magnitude with a consistent fractal area-perimeter relationship. The data are consistent with the predictions of percolation theory for unscreened perimeters and scale-free cluster size distributions and are robust to alterations of the image processing procedure. The small spatial and temporal scales of these data suggest this easily observable system may serve as a useful model for investigating the evolution of pond geometries, while emphasizing the generality of fractal behavior in geophysical surfaces.
    Description: This material is based upon work supported by the National Science Foundation Graduate Research Fellowship Program under Grant No. 2388357, the Gordon and Betty Moore Foundation, and the National Science Foundation, Award No. OCE-1315201.
    Repository Name: Woods Hole Open Access Server
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  • 43
    Publication Date: 2022-05-25
    Description: Author Posting. © The Authors, 2006. This article is posted here by permission of American Physical Society for personal use, not for redistribution. The definitive version was published in Physical Review Letters 96 (2006): 018305, doi:10.1103/PhysRevLett.96.018305.
    Description: We study the liquid-crystalline phase behavior of a concentrated suspension of helical flagella isolated from Salmonella typhimurium. Flagella are prepared with different polymorphic states, some of which have a pronounced helical character while others assume a rodlike shape. We show that the static phase behavior and dynamics of chiral helices are very different when compared to simpler achiral hard rods. With increasing concentration, helical flagella undergo an entropy-driven first order phase transition to a liquid-crystalline state having a novel chiral symmetry.
    Description: M. S. and R. O. are supported by NIH Grant No. EB002583.
    Keywords: Entropy ; Molecular biophysics ; Liquid crystal phase transformations ; Symmetry ; Chirality
    Repository Name: Woods Hole Open Access Server
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  • 44
    Publication Date: 2017-04-04
    Description: We study land subsidence processes and the associated ground fissuring, affecting an active graben filled by thick unconsolidated deposits by means of InSAR techniques and fieldwork. On 21 September 2012, Ciudad Guzmán (Jalisco, Mexico) was struck by ground fissures of about 1.5 km of length, causing the deformation of the roads and the propagation of fissures in adjacent buildings. The field survey showed that fissures alignment is coincident with the escarpments produced on 19 September 1985, when a strong earthquake with magnitude 8.1 struck central Mexico. In order to detect and map the spatio-temporal features of the processes that led to the 2012 ground fissures, we applied InSAR multitemporal techniques to process ENVISAT-ASAR and RADARSAT-2 satellite SAR images acquired between 2003 and 2012. We detect up to 20 mm/year of subsidence of the northwestern part of Ciudad Guzmán. These incremental movements are consistent with the ground fissures observed in 2012. Based on interferometric results, field data and 2D numerical model, we suggest that ground deformations and fissuring are due to the presence of areal subsidence correlated with variable sediment thickness and differential compaction, partly driven by the exploitation of the aquifers and controlled by the distribution and position of buried faults.
    Description: Published
    Description: 8610-8630
    Description: 6A. Monitoraggio ambientale, sicurezza e territorio
    Description: JCR Journal
    Description: open
    Keywords: InSAR ; ground subsidence ; buried faults ; ground fissuring ; 04. Solid Earth::04.01. Earth Interior::04.01.02. Geological and geophysical evidences of deep processes
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 45
    Publication Date: 2017-04-04
    Description: During volcanic eruptions, measurements of the rate at which magma is erupted underpin hazard assessments. For eruptions dominated by the effusion of lava, estimates are often made using satellite data; here, in a case study at Mount Etna (Sicily), we make the first measurements based on terrestrial laser scanning (TLS), and we also include explosive products. During the study period (17–21 July 2012), regular Strombolian explosions were occurring within the Bocca Nuova crater, producing a ~50 m-high scoria cone and a small lava flow field. TLS surveys over multi-day intervals determined a mean cone growth rate (effusive and explosive products) of ~0.24 m3·s−1. Differences between 0.3-m resolution DEMs acquired at 10-minute intervals captured the evolution of a breakout lava flow lobe advancing at 0.01–0.03 m3·s−1. Partial occlusion within the crater prevented similar measurement of the main flow, but integrating TLS data with time-lapse imagery enabled lava viscosity (7.4 × 105 Pa·s) to be derived from surface velocities and, hence, a flux of 0.11 m3·s−1 to be calculated. Total dense rock equivalent magma discharge estimates are ~0.1–0.2 m3·s−1 over the measurement period and suggest that simultaneous estimates from satellite data are somewhat overestimated. Our results support the use of integrated TLS and time-lapse photography for ground-truthing space-based measurements and highlight the value of interactive image analysis when automated approaches, such as particle image velocimetry (PIV), fail.
    Description: Published
    Description: 14967 - 14987
    Description: 3V. Dinamiche e scenari eruttivi
    Description: JCR Journal
    Description: open
    Keywords: lava flow; scoria cone; effusion rate; terrestrial laser scanning; time-lapse photography; Mt. Etna ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring ; 04. Solid Earth::04.08. Volcanology::04.08.07. Instruments and techniques ; 05. General::05.02. Data dissemination::05.02.03. Volcanic eruptions
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 46
    Publication Date: 2017-04-04
    Description: In order to improve the observation capability in one of the most active volcanic areas in the world, Mt. Etna, we developed a processing method to use the surveillance cameras for a quasi real-time mapping of syn-eruptive processes. Following an evaluation of the current performance of the Etna permanent ground NEtwork of Thermal and Visible Sensors (Etna_NETVIS), its possible implementation and optimization was investigated to determine the locations of additional observation sites to be rapidly set up during emergencies. A tool was then devised to process time series of ground-acquired images and extract a coherent multi-temporal dataset of georeferenced map. The processed datasets can be used to extract 2D features such as evolution maps of active lava flows. The tool was validated on ad-hoc test fields and then adopted to map the evolution of two recent lava flows. The achievable accuracy (about three times the original pixel size) and the short processing time makes the tool suitable for rapidly assessing lava flow evolutions, especially in the case of recurrent eruptions, such as those of the 2011–2015 Etna activity. The tool can be used both in standard monitoring activities and during emergency phases (eventually improving the present network with additional mobile stations) when it is mandatory to carry out a quasi-real-time mapping to support civil protection actions. The developed tool could be integrated in the control room of the Osservatorio Etneo, thus enabling the Etna_NETVIS for mapping purposes and not only for video surveillance.
    Description: Published
    Description: 192
    Description: 5V. Sorveglianza vulcanica ed emergenze
    Description: JCR Journal
    Description: open
    Keywords: volcano monitoring ; lava flow mapping ; surveillance camera ; hazard assessment ; geo spatial dataset ; 04. Solid Earth::04.08. Volcanology::04.08.07. Instruments and techniques
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 47
    Publication Date: 2017-04-04
    Description: The 2002-2003 Stromboli eruption triggered the failure of part of the Sciara del Fuoco slope, which generated a tsunami that struck the island and the northern coastline of Sicily. The Sciara del Fuoco is a very steep slope where all lava flows from the craters' emplacement; most lateral eruptions usually take place from fissures propagating in this sector of the volcano. The eruption went on to produce a lava field that filled the area affected by the landslide. This in turn led to further instability, renewing the threat of another slope failure and a potentially related tsunami. This work describes a new joint approach, combining surveying data and aerial image correlometry methods, to study the motion of this unstable slope. The combination has the advantage of very precise surveying measurements, which can be considered the ground truth to constrain the very-high-resolution aerial photogrammetric data, thereby obtaining highly detailed and accurate ground deformation maps. The joint use of the two methods can be very useful to obtain a more complete image of the deformation field for monitoring dangerous and/or rather inaccessible places. The proposed combined methodology improves our ability to study and assess hazardous processes associated with significant ground deformation.
    Description: This Research has been supported by the Spanish Ministry of Economy and Competitiveness research projects AYA2010-17448 and ESP2013-47780-557 C2-1-R, and the EU 7th FP MED-SUV project (contract 308665). It is a contribution to the Moncloa Campus of International Excellence
    Description: Published
    Description: 463
    Description: 1V. Storia e struttura dei sistemi vulcanici
    Description: JCR Journal
    Description: open
    Keywords: surveying ; data integration ; aerial photogrammetry ; monitoring ; flank instability ; sector collapse ; landslide ; tsunami ; volcanoes ; 04. Solid Earth::04.08. Volcanology::04.08.07. Instruments and techniques
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 48
    Publication Date: 2017-04-04
    Description: We applied the Small Baseline Subset multi-temporal InSAR technique (SBAS) to two SAR datasets acquired from 2003 up to 2013 by Envisat (ESA, European Space Agency) and COSMO-SkyMed (ASI, Italian Space Agency) satellites to investigate spatial and temporal patterns of land subsidence in the Sibari Plain (Southern Italy). Subsidence processes (up to ~20 mm/yr) were investigated comparing geological, hydrogeological, and land use information with interferometric results. We suppose a correlation between subsidence and thickness of the Plio-Quaternary succession suggesting an active role of the isostatic compensation. Furthermore, the active back thrusting in the Corigliano Gulf could trigger a flexural subsidence mechanism even if fault activity and earthquakes do not seem play a role in the present subsidence. In this context, the compaction of Holocene deposits contributes to ground deformation. Despite the rapid urbanization of the area in the last 50 years, we do not consider the intensive groundwater pumping and related water table drop as the main triggering cause of subsidence phenomena, in disagreement with some previous publications. Our interpretation for the deformation fields related to natural and anthropogenic factors would be a comprehensive and exhaustive justification to the complexity of subsidence processes in the Sibari Plain.
    Description: PON (Operational National Plan) 2007–2013 from MIUR (Italian Research Ministry of Research) Project AMICUS (Study for the environmental protection and the mitigation of Anthropogenic Pollution In the Coastal Environment of selected areas of Calabria; ID: PON01_ 02818) - COSMO-SkyMed® PRODUCTS, © ASI (Italian Space Agency)—provided under license of ASI in the framework of the S3 Project “Short term earthquake prediction and preparation” (DPC-INGV, 2013). The Envisat images are provided by ESA (European Space Agency) under the CAT.1P 5605
    Description: Published
    Description: 16004–16023
    Description: 6A. Monitoraggio ambientale, sicurezza e territorio
    Description: 1IT. Reti di monitoraggio e Osservazioni
    Description: JCR Journal
    Description: restricted
    Keywords: SBAS-InSAR ; Sibari Plain ; subsidence ; geology ; anthropic processes ; 04. Solid Earth::04.03. Geodesy::04.03.07. Satellite geodesy
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 49
    Publication Date: 2022-05-26
    Description: © The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Derr, N. J., Fronk, D. C., Weber, C. A., Mahadevan, A., Rycroft, C. H., & Mahadevan, L. Flow-driven branching in a frangible porous medium. Physical Review Letters, 125(15), (2020): 158002, doi:10.1103/PhysRevLett.125.158002.
    Description: Channel formation and branching is widely seen in physical systems where movement of fluid through a porous structure causes the spatiotemporal evolution of the medium. We provide a simple theoretical framework that embodies this feedback mechanism in a multiphase model for flow through a frangible porous medium with a dynamic permeability. Numerical simulations of the model show the emergence of branched networks whose topology is determined by the geometry of external flow forcing. This allows us to delineate the conditions under which splitting and/or coalescing branched network formation is favored, with potential implications for both understanding and controlling branching in soft frangible media.
    Description: N. D. was partially supported by the NSF-Simons Center for Mathematical and Statistical Analysis of Biology at Harvard, Grant No. 1764269, and the Harvard Quantitative Biology Initiative. C. H. R. and N. D. were partially supported by the National Science Foundation under Grant No. DMS-1753203. C. H. R. was partially supported by the Applied Mathematics Program of the U.S. DOE Office of Science Advanced Scientific Computing Research under Contract No. DE-AC02-05CH11231. L. M. was partially supported by the National Science Foundation under Grants No. DMR-2011754 and No. DMR-1922321.
    Repository Name: Woods Hole Open Access Server
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  • 50
    Publication Date: 2023-02-22
    Description: 7 Figures, 20 pages
    Description: The search of hardware-compatible strategies for solving NP-hard combinatorial optimization problems (COPs) is an important challenge of today s computing research because of their wide range of applications in real world optimization problems. Here, we introduce an unconventional scalable approach to face maximum satisfiability problems (Max-SAT) which combines probabilistic computing with p-bits, parallel tempering, and the concept of invertible logic gates. We theoretically show the spintronic implementation of this approach based on a coupled set of Landau-Lifshitz-Gilbert equations, showing a potential path for energy efficient and very fast (p-bits exhibiting ns time scale switching) architecture for the solution of COPs. The algorithm is benchmarked with hard Max-SAT instances from the 2016 Max-SAT competition (e.g., HG-4SAT-V150-C1350-1.cnf which can be described with 2851 p-bits), including weighted Max-SAT and Max-Cut problems.
    Description: Published
    Description: 024052
    Description: 3IT. Calcolo scientifico
    Description: JCR Journal
    Keywords: Physics - Mesoscopic Systems and Quantum Hall Effect; Physics - Mesoscopic Systems and Quantum Hall Effect
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 51
    Publication Date: 2024-04-30
    Description: Current understanding of the kinetic-scale turbulence in weakly collisional plasmas still remains elusive. We employ a general framework in which the turbulent energy transfer is envisioned as a scale-to-scale Langevin process. Fluctuations in the sub-ion range show a global scale invariance, thus suggesting a homogeneous energy repartition. In this Letter, we interpret such a feature by linking the drift term of the Langevin equation to scaling properties of fluctuations. Theoretical expectations are verified on solar wind observations and numerical simulations, thus giving relevance to the proposed framework for understanding kinetic-scale turbulence in space plasmas.
    Description: Published
    Description: L042014
    Description: OSA3: Climatologia e meteorologia spaziale
    Description: JCR Journal
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  • 52
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    The Journal of Chemical Physics 113 (2000), S. 7621-7626 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: When placed into an external magnetic field inhomogeneous porous structures, like rocks, cement gels, ceramics, etc., exhibit strong local magnetic field gradients (LMFG), which are inherently related with the size, shape, and distribution of their pores. In this paper, we present a method of measuring LMFG in a liquid-filled porous media, provided that the fast exchange model sufficiently describes water motion in the pores, which is based solely on the measurement of the water 1H NMR spin lattice relaxation rates and the knowledge of the unrestricted diffusion coefficient. The method is applied to two hydrating white cement samples with different hydration kinetics, and the results are correlated with the time evolution of the pore structure. It is shown that the measured LMFG have extremely high values, which qualitatively reflect the sharp needlelike morphology of the internal cement gel surface. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 7627-7634 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: By use of optical steady state and time resolved spectroscopy, we studied the evolution of the triplet excited state in a series of six ethynylenic polymers of the structure [-Pt(PBu3n)2-C(Triple Bond)C-R-C(Triple Bond)C-]n where the spacer unit R is systematically varied to give optical gaps from 1.7–3.0 eV. The inclusion of platinum in the polymer backbone induces a strong spin-orbit coupling such that triplet state emission (phosphorescence) associated with the conjugated system can be detected. Throughout the series we find the S1-T1 (singlet-triplet) energy splitting to be independent of the spacer R, such that the T1 state is always 0.7±0.1 eV below the S1 state. With decreasing optical gap, the intensity and lifetime of the triplet state emission were seen to reduce in accordance with the energy gap law. © 2000 American Institute of Physics.
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  • 54
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    The Journal of Chemical Physics 113 (2000), S. 7511-7518 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A modified conductorlike screening continuum solvation model, implemented in the quantum chemistry program GAMESS, has been extended to second order perturbation theory (MP2). Two possible schemes have been considered: (a) the calculation of the MP2 energy using the solvated Hartree–Fock (HF) orbitals, and (b) the implementation of a double-iterative procedure where the HF density is updated with respect to the MP2 surface charges. The influence of the self-consistency of the surface charge distribution with respect to the MP2 density has been analyzed for a small dataset of 21 neutral molecules and 13 ions. In addition, the details of the distribution of surface charge density (σ profiles) and the effects of electron correlation on the accuracy of such distributions is analyzed in terms of the overall concept of deviation of continuum models from dielectric theory, leading to insights into higher order models. © 2000 American Institute of Physics.
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  • 55
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    The Journal of Chemical Physics 113 (2000), S. 7519-7529 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The conductorlike continuum solvation model, modified for ab initio in the quantum chemistry program GAMESS, implemented at the Møller–Plesset Order 2 (MP2) level of theory has been applied to a group of push–pull pyrrole systems to illustrate the effects of donor/acceptor and solvation on the stability and energetics of such systems. The most accurate theoretical gas and solution phase data to date has been presented for the parent furan-2-carbaldehyde (furfural) system, and predictions made for three additional analogues, thiophene-2-carbaldehyde, pyrrole2-carbaldehyde, and, cyclopentadiene-1-carbaldehyde. Solvent effects on internal rotational barriers in all systems were evaluated over six different values of dielectric, using the new method. Calculated electrostatic energies are shown to be highly sensitive to level of theory incorporated. © 2000 American Institute of Physics.
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  • 56
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    The Journal of Chemical Physics 113 (2000), S. 7554-7563 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Exploiting an electrostatic analogy, we show that the elastic forces between a set of rigid particles embedded in a phantom polymer network can be represented by a simple bead-and-spring model. The beads represent the particles and the springs the rubber matrix. The model is validated by Monte Carlo simulation of rubbers filled with hard spherical particles, at volume fractions between 0.1 and 0.3. We derive both the moduli and the full stress–strain curves, under uniaxial elongation. The model reproduces and extends previous theoretical results on the so-called hydrodynamic reinforcement effect. © 2000 American Institute of Physics.
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  • 57
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    The Journal of Chemical Physics 113 (2000), S. 7571-7577 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The temperature dependence of electron transmission through various organized organic thin films (OOTFs) was investigated. For most systems a strong dependence of the transmission efficiency on temperature was observed, even for a relatively small temperature range. The well defined structure of the OOTFs and the monitoring of the angular dependence of both the initial and the final velocities of photoelectrons were used to reveal the mechanism behind the temperature effect and further elucidate the transmission mechanism. A simple model, which assumes that the electron transmission yield is much higher along the organic chains than in any other direction, was able to reproduce the experimental observations. We find that the photoelectron transmission yield through OOTFs is extremely sensitive to the structural order in the film. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 7546-7553 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Femtosecond vibrational wave-packet dynamics in a cyanine molecule is observed to be strongly dependent on the chirp direction of the excitation pulse. The slow-decay component associated with an oscillatory structure, which corresponds to the excited-state lifetime and a vibrational mode of 160±10 cm−1, respectively, is measured by the femtosecond time-resolved transmission spectroscopy. The excited-state population is substantially decreased and enhanced in the cases of negatively chirped (NC) and positively chirped (PC) excitations, respectively. A quantum mechanical calculation by means of the split operator scheme is performed to reproduce the wave-packet propagation after the chirped pulse excitation. The calculation shows that the spatial distribution of the wave packet for the NC case is narrower than that for the PC case during the excitation, and that the overlap integral between the excited- and ground-state wave packets determines the efficiency of the population dumping. © 2000 American Institute of Physics.
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  • 59
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    The Journal of Chemical Physics 113 (2000), S. 7564-7570 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Metastable impact electron spectroscopy (MIES) and ultraviolet photoelectron spectroscopy are used in this study to investigate low-defect and defective MgO(100) thin films. Unlike low-defect films, defective films exhibit a new spectroscopic feature located ∼2 eV above the top of valence band. Exposing the defective film to oxygen quenches the emission of electrons from F centers created on the surface and in the subsurface regions. Extended defects, unseen in the MIES spectra of the clean surface, are detectable using NO titration. MIES and thermal programmed desorption indicate that at ∼100 K NO adsorbs dissociatively on defects, forming N2O. Only a small fraction of the MgO surface becomes covered with N2O at ∼100 K for the low-defect MgO film indicating that N2O molecules preferentially adsorb on the extended defects. The saturation coverage of N2O increases appreciably for the defective sample. © 2000 American Institute of Physics.
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  • 60
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    The Journal of Chemical Physics 113 (2000), S. 7530-7545 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The Yang–Yang relation expresses the heat capacity at constant volume, CV(T,ρ), of a fluid linearly in terms of the second temperature derivatives of the pressure and the chemical potential, p″(T,ρ) and μ″(T,ρ). At a gas–liquid critical point CV diverges so, on approaching Tc from below, either pσ″(T), or μσ″(T), or both must diverge, where the subscript σ denotes the evaluation of p and μ on the phase boundary or vapor-pressure curve. However, previous theoretical and experimental studies have suggested that μσ″(T) always remains finite. To test these inferences, we present an analysis of extensive two-phase heat capacity data for propane recently published by Abdulagatov and co-workers. By careful interpolation in temperature and subsequently making linear, isothermal fits vs specific volume and vs density, we establish that the divergence is shared almost equally between the derivatives pσ″(T) and μσ″(T). A re-examination of the analysis of Gaddy and White for carbon dioxide leads to similar conclusions although the singular contribution from μσ″(T) is found to be of opposite sign and probably somewhat smaller than in propane. © 2000 American Institute of Physics.
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  • 61
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    The Journal of Chemical Physics 113 (2000), S. 7578-7581 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Circular-difference effects in second-harmonic generation have been used to study chiral, anisotropic thin films of a helicene derivative. For such samples, these effects arise both from the chirality of the film and from its anisotropy. We show theoretically and experimentally that there is a fundamental difference between a circular-difference effect originating from chirality and anisotropy. A method is described that distinguishes the two contributions. © 2000 American Institute of Physics.
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  • 62
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    The Journal of Chemical Physics 113 (2000), S. 7588-7592 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Recent molecular dynamics data on the diffusion of linear diatomic and triatomic molecules in the zeolite silicalite are analyzed in terms of a new correlated model [F. Jousse, S. M. Auerbach, and D. P. Vercauteren, J. Chem. Phys. 112, 1531 (2000)] capable to account for both first- and higher-order correlation effects. This "N-step" model reproduces very well our calculated mean square displacements and diffusion coefficients of the molecules considered. The improvements with respect to the results obtained with our previous "two-step" model [P. Demontis, J. Kärger, G. B. Suffritti, and A. Tilocca, Phys. Chem. Chem. Phys. 2, 1455 (2000)] are remarkable for all molecules except chlorine, showing that only in this case the effect of (negative) correlations spanning more than two jumps between channel intersections (∼20 Å) can be neglected. The basic trajectory analysis in terms of single- and two-step models, besides being an useful reference, provides all the input data needed for the application of the N-step model. Indeed, in its silicalite formulation, the N-step model is strongly linked to the two-step one because it calculates the probability of a sequence of jumps in the same channel by means of the correlations between any two consecutive jumps. Finally, the possibility to obtain qualitative insight into the diffusive mechanism through various kind of correlation coefficients is discussed. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 7598-7605 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A model is developed that describes bimolecular recombination of photogenerated carriers in two dimensional systems. Carriers are free to diffuse in two dimensions and undergo bimolecular recombination, while drifting under the influence of an electric field in the third dimension. The model describes a competition between carrier loss due to transiting and loss due to bimolecular recombination. This model of recombination quenching is then used to obtain information on microscopic parameters associated with photogeneration efficiency and charge transport in organic quantum wells formed from Langmuir Blodgett films of conjugated molecules. The ratio of the intralayer to interlayer tunneling rates is found along with the quantum efficiency for photocarrier generation for two bis-phthalocyanine amphiphilic molecules. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 7593-7597 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Films of pure polyaniline and polyaniline-tetracyanoquinodinodimethane have been prepared. The optical absorption spectra of both the samples in the emeraldine base forms are explained in light of the three-dimensional exciton model. A temperature dependence study of the electrical conductivity of the samples shows an interesting crossover phenomenon (Tc=143 K) which may be considered as competition of the two opposingly directed factors, namely, charge transfer interaction and the disorderness parameter (r). While charge transfer interaction is evident from optical absorption spectroscopy, the extent of disorderness is reflected by the results of CHN microanalysis and temperature dependent electrical conductivity measurement. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 7582-7587 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: In this investigation we use B3LYP density functional theory (DFT) to investigate the CVD growth mechanism of (100) diamond. Our results are consistent with the Garrison mechanism in which the dimer-opening step involves simultaneous formation of a surface olefin and dissociation of the dimer. We calculate this step to have a barrier of 9.6 kcal/mol. The olefin is then attacked by a surface radical to form a six-membered ring. We find this reaction to be the rate-limiting step with an activation energy of 13.6 kcal/mol. This is in excellent agreement with the experimental value of 15 kcal/mol obtained by the selective growth method and XPS. The direct ring-opening and ring-closing reaction from adsorbed CH2 radical has an activation energy of 49.4 kcal/mol and does not contribute significantly to the growth rate. The barrier on larger clusters that include the effects of neighboring adsorbed hydrogen increases to 15.6 kcal/mol. Additionally, our calculated vibrational frequencies agree within 2% of experimental IR and HREELS spectra. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 7606-7612 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The tunneling rate of photocreated charge carriers between layers in Langmuir–Blodgett multilayer structures is measured indirectly using the novel technique of bimolecular recombination quenching. The tunneling rate is demonstrated to be dependent upon the applied electrostatic potential difference between the layers. This dependence is explored in light of the Marcus theory of charge transfer. That theory was developed to describe redox reactions where the driving force is supplied by a chemical potential difference between two chemically different parts of a more complex system. In the current work the electrostatic potential replaces the chemical potential as the driving potential. The field dependence of the exciton dissociation probability is also determined. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 7613-7620 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The tunneling rate of photocreated charge carriers between layers in Langmuir–Blodgett multilayer structures is measured indirectly using the novel technique of bimolecular recombination quenching. The tunneling rate is measured as a function of the applied electrostatic potential difference between the layers as the temperature is varied between 300 and 4 K. This dependence is examined in light of the Marcus theory of charge transfer where the electrostatic potential replaces the chemical potential as the driving potential. The expectations of the Marcus theory are not met and the rate is effectively temperature independent, contrary to expectation. Other mechanisms are explored that may explain the lack of temperature dependence including the role of high frequency vibrations and the role of the zero point energy of those vibrations. The temperature dependence of the exciton dissociation probability is also examined. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 6652-6659 
    ISSN: 1089-7690
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The equilibrium constants for water oligomers ranging from dimers to cyclic hexamers are determined using Wertheim's theory of associating systems. In the present model for water, the pair potential has a spherical hard core, and tetrahedral hydrogen bonds which are represented by an energy parameter and an interaction volume. On the basis of the present theory, one predicts that in earth's troposphere, water dimers and perhaps trimers may contribute to the absorption of solar radiation, but concentrations of higher oligomers are too low to influence the optical properties of the earth's atmosphere. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 6673-6676 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Steric effect in the Penning ionization reaction of Ar*(3P2,0)+CHCl3→Ar+CHCl2++Cl+e− was directly observed at an average collision energy of 0.13 eV using the oriented CHCl3 molecular beam. The product CHCl2+ ions are measured for the H-end, the CCl3-end, and sideways orientations. The obtained steric opacity function reveals that the CCl3-end orientation is more favorable than the H-end orientation, and the sideways approach is found to be more favorable than the collinear approaches from both ends of the molecule. Furthermore, we confirm the good correlation between Penning ionization anisotropy and the electron density distribution of the 2a2 HOMO orbital of the CHCl3 molecule, whose electron cloud is mostly localized around the sideways. These results substantiate the electron exchange mechanism which is commonly accepted for the Penning ionization reaction, where the overlap of projectile atomic and target molecular orbital plays a key role in Penning ionization efficiency. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 6677-6686 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The potential-energy curves for the X 1Σg+, a 1Πg, a′ 1Σu−, w 1Δu, c3 1Πu, and b 1Πu states of N2 have been investigated in full configuration interaction (FCI) and coupled-cluster response calculations. The equilibrium bond lengths, adiabatic excitation energies, and harmonic frequencies have been obtained with the coupled-cluster singles model (CCS), an approximate coupled-cluster singles and doubles model (CC2), the coupled-cluster singles and doubles model (CCSD), and an approximate coupled-cluster singles, doubles, and triples model (CC3), and subsequently compared to FCI results. The weak and strong features of the coupled-cluster models are discussed and illustrated. Overall, improvements towards FCI are obtained in the hierarchy CCS–CC2–CCSD–CC3. CC3 is always consistently better than CCSD, and for all the considered spectroscopic constants CC3 provides excellent results. Examples where the CC3 model fails are also given. The noniterative triples model, CCSDR(3), is compared to the iterative triples models CC3 and FCI. CCSDR(3) recovers the major part of the CC3 correlation contribution and is thus a cheap alternative to the CC3 model. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 6660-6672 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Photodissociation and recombination of an F2 molecule embedded in an Ar cluster is investigated. The electronic states involved are described by the valence bond approach for the F(2P)+F(2P) interaction, with spin–orbit coupling included and the anisotropic interactions between F and Ar atoms described by the diatomics-in-molecules (DIM) approach. The potential energy surfaces for 36 electronic states and the nonadiabatic couplings between them are constructed in this basis. The surface hopping method is used for dynamical simulations. The main results are: (i) Spin nonconserving transitions play a crucial role both in the dissociation and in the recombination dynamics. (ii) The ratio between the population of the triplet states and the population of the singlet states reaches the statistical equilibrium value of 3:1 60 fs after the photoexcitation, but the population of specific singlet and triplet states remains nonstatistical for at least 1.5 ps. (iii) Recombination on the only bound excited state (3Πu) becomes significant within 100 fs and builds up to 40% of the trajectories within 1 ps after excitation of the cluster with 4.6 eV. This is in accord with recent experiments on ClF/Ar solid, where strong emission from this state was found. (iv) 3% of recombination on the ground 1Σg state is found as well. (v) For excitation energy of 4.6 eV, the dissociation can be direct or delayed. In delayed dissociation the F photofragments hit the Ar cage more than once before escaping the cage. (vi) For excitation energy of 6.53 eV the yield of dissociation was found to be 100%, and the dissociation is direct only. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 6687-6701 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: A new ab initio pair potential for water was generated by fitting 2510 interaction energies computed by the use of symmetry-adapted perturbation theory (SAPT). The new site–site functional form, named SAPT-5s, is simple enough to be applied in molecular simulations of condensed phases and at the same time reproduces the computed points with accuracy exceeding that of the elaborate SAPT-pp functional form used earlier [J. Chem. Phys. 107, 4207 (1997)]. SAPT-5s has been shown to quantitatively predict the water dimer spectra, see the following paper (paper II). It also gives the second virial coefficient in excellent agreement with experiment. Features of the water dimer potential energy surface have been analyzed using SAPT-5s. Average values of powers of the intermolecular separation—obtained from the ground-state rovibrational wave function computed in the SAPT-5s potential—have been combined with measured values to obtain a new empirical estimate of the equilibrium O–O separation equal to 5.50±0.01 bohr, significantly shorter than the previously accepted value. The residual errors in the SAPT-5s potential have been estimated by comparison to recent large-scale extrapolated ab initio calculations for water dimer. This estimate—together with the dissociation energy D0 computed from SAPT-5s—leads to a new prediction of the limit value of D0 equal to 1165±54 cm−1, close to but significantly more accurate than the best empirical value. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 6702-6715 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Nearly exact six-dimensional quantum calculations of the vibration–rotation–tunneling (VRT) levels of the water dimer for values of the rotational quantum numbers J and K ≤2 show that the SAPT-5s water pair potential presented in the preceding paper (paper I) gives a good representation of the experimental high-resolution far-infrared spectrum of the water dimer. After analyzing the sensitivity of the transition frequencies with respect to the linear parameters in the potential we could further improve this potential by using only one of the experimentally determined tunneling splittings of the ground state in (H2O)2. The accuracy of the resulting water pair potential, SAPT-5st, is established by comparison with the spectroscopic data of both (H2O)2 and (D2O)2: ground and excited state tunneling splittings and rotational constants, as well as the frequencies of the intermolecular vibrations. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 6716-6723 
    ISSN: 1089-7690
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The group of three lowest singlet C 1s-excited states of formaldehyde H2CO is studied theoretically. The equilibrium geometries are determined at the restricted open-shell Hartree–Fock (ROHF) level and refined total energies are obtained using the multireference configuration interaction (MRCI) approach. In agreement with an earlier prediction [Chem. Phys. 122, 9 (1988)] the second lowest singlet state, 1B2, is characterized by a doubly excited, "two particle–two hole" (2p–2h), configuration C 1s,n→π*2. Our calculations predict that H2CO in the 1B2(2p–2h) state has a stable pyramidal equilibrium structure with a barrier to inversion of 0.28 eV, the valence angle being close to 107°. The calculated length of the CO bond is 1.390 Å. The 1B2(2p–2h) state is shown to be also bound with respect to all possible dissociation and rearrangement processes. The lowest predicted dissociation energy for the 1B2 state (H2CO*→H2+CO* reaction) is 0.29 eV (6.69 kcal/mol). The rationalization of the great stability of the 1B2(2p–2h) state is the similarity of its electronic structure to that of the first singly-excited state 2A″(n) of nitroxyl radical H2NO⋅. The neighboring states 1B1(C 1s→π*) and 1A1(C 1s→3s) are characterized within the same framework. Spectroscopic implications and possibilities for the experimental identification of the 1B2(2p–2h) state are discussed. © 2000 American Institute of Physics.
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    Notes: A general nonorthogonal coupled electron pair approach for the evaluation of electron correlation contribution is presented in details. The self-consistent field for molecular interactions wave function is used as reference state for a multistructure valence bond (VB) calculation. The central idea of the method is the optimization of the virtual space of the VB wave function by means of a procedure very close to the independent electron pair approach (IEPA) scheme. All the orbitals employed are expanded in the basis set of their fragment so as to exclude the basis set superposition error (BSSE) in a priori fashion. As an example, the application to the study of the van der Waals complex He–CH4 is reported. The equilibrium geometry of the system occurs at a He–C distance of 3.6 Å , with the He atom pointing to the center of one of the faces of the CH4 molecule, with a well depth of 19 cm−1. The potential energy surface of the He–CH4 complex is used to determine the parameters of a potential model which is employed in close-coupling calculations of integral state-to-state cross sections for rotationally inelastic scattering of methane molecules with helium atoms. The predicted values are compared with the available experimental data. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 6736-6747 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: An ab initio study of the ground potential energy surface (PES) of the O(1D)+H2O system has been performed, employing Møller–Plesset methods. From the stationary and additional points calculated, the ground PES has been modeled as a triatomic system, with an OH group of the H2O molecule treated as a single atom of 17.0 amu. The rate constant of reaction (1), O(1D)+H2O→2OH (main reaction channel), estimated from the quasiclassical trajectory (QCT) calculations is reasonably close to the recommended experimental value. For the relative translational energies explored (ET=0.234, 0.303, and 0.443 eV) and H2O at T=300 K, the QCT OH vibrational populations are in good agreement with the experimental values reported for the new OH fragment, but the QCT OH average rotational energies are in general quite larger than the experimental ones. Regarding the stereodynamics, for ET=0.234 eV there is not a clear tendency to a particular rotational alignment of the OH product with respect to the initial relative velocity vector, in agreement with experiments. The QCT results also show that nearly all reactive trajectories leading to reaction (1) take place through an insertion microscopic mechanism, which, even at the highest ET value considered (0.443 eV), is mainly (70%) a nondirect one. The collision complex has an average lifetime of about three rotational periods and a geometry around that of the HO(OH) hydrogen peroxide molecule. The QCT results concerning the microscopic mechanism of reaction (1) are in agreement with the suggested ones by the experimentalists to interpret their results. The present study should be considered as a starting point in the study of reaction (1) from which different aspects on the dynamics may be learned. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 6782-6787 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: A molecular dynamics simulation of molten ZnCl2 with a realistic interionic potential is used to evaluate the contribution of interaction-induced dipoles to the dielectric response, or equivalently, to the conductivity. The induced dipoles are included self-consistently in the interionic potential. The contribution is found to be significant across the accessible range of frequencies, modifying various features of the spectrum ordinarily attributed to elementary translations of the ionic charges, and markedly improving agreement with experimental spectra. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 6774-6781 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Homogeneous nucleation rates of n-pentanol in nitrogen are presented. They are obtained from a piston-expansion tube (pex-tube) involving the nucleation pulse method which generates a limited number of nuclei that grow into droplets. The detection of the droplets is achieved by a new counting method developed on the basis of a CCD camera in combination with a laser light sheet. Nucleation rates between 104 and 109 cm−3 s−1 are covered for three nucleation temperatures 250, 260, and 270 K. The rates are plotted as isotherms vs supersaturation. Influence of the initial expansion temperature and the nucleation pressure on the nucleation rate is identified. Comparison with results available in literature and classical nucleation theory (CNT) is provided. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 6748-6759 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: A previously reported potential energy surface (PES) and a new barrierless PES (both based on ab initio data and describing the CH3 group as a pseudoatom) were used to study the O(1D)+CH4→OH+CH3 reaction with the quasiclassical trajectory (QCT) method. The new PES accurately reproduces the experimental rate constant values, in contrast to the previous PES. The QCT study was mainly performed at the relative translational energy (ET) resulting from the photodissociation of N2O at 193 nm (〈ET〉=0.403 eV), although the collision energy obtained from the photodissociation of O3 at 248 nm (〈ET〉=0.212 eV) was also considered. Good agreement between theory and experiment was obtained for the OH vibrational populations and for the OH rotational populations for the v′≥2 vibrational levels, while the rotational distributions for v′=0–1 are more excited than in the experiment. The QCT results at ET=0.403 eV satisfactorily reproduce the experimental kk′ angular distribution of the state-specific channel OH(v′=4, N′=8) and the corresponding ET′ distribution. For OH(v′=0, N′=5) the reproduction of these properties is poorer, especially for the ET′ distribution. At 0.403 eV the contribution of the abstraction mechanism to the reaction mode is negligible and two insertion like mechanisms (with fast or slow elimination) are found to be predominant, as suggested experimentally. The discrepancies observed between the QCT and experimental results can be explained on the basis of the defective description of the insertion/slow elimination mechanism provided by the model. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 6760-6773 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Resonance Raman spectra are presented for the nitrate anion, NO3−, in water, ethylene glycol, methanol, and acetonitrile solution at six excitation wavelengths from 246 to 204 nm, on resonance with the lowest π→π* excitation. Absolute Raman cross sections for the CH stretches of ethylene glycol and methanol at these wavelengths are also reported. The nitrate spectra in all four solvents are dominated by fundamentals, overtones, and combination bands of the totally symmetric NO stretch (ν1) near 1043 cm−1 and the out-of-phase NO stretches (ν3) at 1340–1400 cm−1, consistent with substantial changes in NO bond length upon π-electron excitation. The intensity in ν3 and the (approximate)60 cm−1 splitting of this nominally degenerate vibration are indicative of pronounced breaking of the isolated molecules D3h symmetry by the local solvent environment. Intensity in the overtone of the out-of-plane mode (ν2) near 830 cm−1 suggests a change in the equilibrium geometry from planar to pyramidal upon electronic excitation. The absorption spectra and absolute Raman cross sections are simulated with a model that considers resonance with two orthogonally polarized electronic states whose degeneracy is broken by the locally asymmetric environment. Both solvent reorganization and geometry changes along the nitrate molecular vibrations make major contributions to the breadth of the absorption band. No differences between resonant and nonresonant linewidths are observed for the ν1 band. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 6788-6794 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: High resolution neutron powder diffraction experiments on NaDS and KDS were carried out as a function of temperature between T=4 K and T=470 K at ROTAX (ISIS, UK). The probability density function (pdf) of the atoms was studied in detail, in particular that of deuterium. Several forms of temperature dependent reorientational disorder of the anions are the reason for structural polymorphism of these compounds. A monoclinic low (LTM), a rhombohedral middle (MTM), and a cubic high temperature (HTM) modification are the polymorphs. For the structures of the different modifications the parameters were refined by the use of split-atom models, Fourier synthesis, and/or cubic harmonics. As a main result of this study the anisotropy of the pdf of deuterium in NaDS and KDS was evaluated. It is due to large amplitudes of librations of the anions. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 6815-6821 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The self-consistent integral equation method is applied to calculate the structure and the thermodynamic properties of supercritical argon considered in a recent neutron-scattering experiment by Pfleiderer et al. [J. Chem. Phys. 111, 2641 (1999)]. Two kinds of potentials, different in nature, are used for the calculations. One is an empirical standard potential and the other is founded upon ab initio quantum chemical calculations. The small discrepancies between the two approaches are discussed, and the results are compared to the recent measurements for structure and experimental thermodynamic properties as well. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 6795-6802 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: We describe a new type of solid effect for dynamic nuclear polarization (DNP) that is based on simultaneous, near resonant microwave (mw) and radio frequency (rf) irradiation of a coupled electron nuclear spin system. The interaction of the electron spin with the mw field is treated as an electron spin dressed state. In contrast to the customary laboratory frame solid effect, it is possible to obtain nuclear polarization with the dressed state solid effect (DSSE) even in the absence of nonsecular hyperfine coupling. Efficient, selective excitation of dressed state transitions generates nuclear polarization in the nuclear laboratory frame on a time scale of tens of μs, depending on the strength of the electron–nuclear coupling, the mw and rf offset and field strength. The experiment employs both pulsed mw and rf irradiation at a repetition rate comparable to T1e−1, where T1e is the electronic spin lattice relaxation time. The DSSE is demonstrated on a perdeuterated BDPA radical in a protonated matrix of polystyrene. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 6803-6814 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The aqueous solutions of CsCl were studied at room temperature by infrared (IR) spectroscopy in the entire solubility range, 0–1200 g/L, using attenuated total reflection (ATR) sampling. The influence of anomalous dispersion on the IR–ATR spectra was evaluated by calculating the imaginary refractive index, k(ν), of each sample. Factor analysis (FA) was used to determine the number and abundance of species in the solutions. FA applied to both k(ν) spectra and IR-ATR spectra produced two principal spectra with a similar abundance of species. This result indicates that, even at high salt concentration, the optical effects do not influence the chemical analysis of IR–ATR spectra. The spectral modifications related to the salt concentrations are mainly first order. Second order effects were observed, but being weak, were not investigated. The two principal spectra are related to the two species present in the solution: pure water and CsCl–solvated water. From the latter, 2.8±0.4 water molecules were calculated to be associated with each close-bound Cs+/Cl− ion pair. In the case of KCl and NaCl aqueous solutions, both of which showed the same number of species, the number of water molecules associated to an ion pair was 5.0±0.4. That the latter number is different from that of CsCl indicates that the interaction between water molecules and ion pairs is different when cation Na or K in the chloride salt is replaced by Cs. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 6822-6830 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: We consider a nucleating center consisting of both an insoluble core and soluble species and develop the thermodynamics of isothermal formation of a droplet on such a nucleus in a multicomponent vapor mixture. Two different approaches to the derivation of the free energy of droplet formation within the framework of the capillarity approximation are considered. If condensation is not barrierless, the free energy of formation describes a multidimensional free-energy surface having a "well" point and a "saddle" point. It is shown that in a strict theory, taking account of surface enrichment effects, the compositions of droplets corresponding to these two points are equal and can be found without knowing the surface tension of the droplet. For the case of no surfactants in the droplet, we extend the Kuni method of investigating the behavior of the free energy of droplet formation to the case of heterogeneous multicomponent condensation on mixed nuclei, which makes it possible to find out all the main features of the free-energy surface without explicitly knowing the free-energy itself. The theoretical results are illustrated by numerical calculations for the water–methanol condensation on mixed nuclei. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 6851-6863 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: A classical molecular dynamics simulation of liquid benzene is performed, using a potential model which allows for full molecular flexibility. The short range intermolecular radial distribution function is on average reminiscent of the crystalline structure, although practically no preferential orientation can be found for the molecules in the first coordination shell. The average cage lifetime and its vibrational dynamics are obtained from appropriate time correlation functions. The intramolecular vibrations are investigated by calculating the vibrational density of states and the infrared and Raman spectra, achieving an excellent agreement with the experimental data. Finally, the dephasing of the ν1(A1g) ring breathing mode and of the ν6(E2g) in-plane bending mode is analyzed on the basis of the Kubo dephasing function. For ν1 mode the Kubo correlation time of 516 fs agrees with the experimental value, and is consistent with a relaxation mechanism involving the cage reorganization. In contrast, ν6 has a practically pure Lorentzian line shape, with a width of 7.16 cm−1 in perfect agreement with the experimental value of 7.2 cm−1. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 6831-6850 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: We present a microscopic model of carbon monoxide (CO) binding to myoglobin which reproduces the experimentally observed Arrhenius pre-exponential factor of 109 s−1 and activation enthalpy distribution centered at 12 kJ/mol. The model is based on extensive ab initio calculations of CO interacting with a model heme-imidazole group which we performed using a fully quantum mechanical Hartree–Fock/density functional theory (HF/DFT) hybrid method. We fit the HF/DFT calculated energies, obtained for over 1000 heme-CO structures with varied CO and iron positions and orientations for both high (S=2) and low (S=0) spin states, to a model potential function which includes a bonding interaction in both of the spin states, electrostatic, and anisotropic Lennard-Jones-type interactions. By combining the x-ray determined protein structure with this potential and protein-CO interactions and internal heme interaction potentials obtained from established molecular dynamics literature, we calculate the energy required for the CO to reach the spin crossing from the heme pocket. We find that the transition between the two spin states occurs when CO and iron have activation enthalpies of 8 kJ/mol and 3 kJ/mol, respectively, which are necessary to move CO towards the iron and the iron atom relative to the heme plane Npyr. At the same time we find that 1 kJ/mol is needed to move Nε of His-64 and Cγ of Val-68 relative to the heme group. The requirement that these motions be synchronized reduces the Arrhenius pre-exponential by a factor of 150 from the 1012 s−1 obtained from CO motion across the heme pocket, leaving a factor of ∼ 6 to account for CO orientation and nonadiabaticity of the electronic spin change. The observed width of the enthalpy distribution is reproduced by assuming a Gaussian distribution of the heme positions with a standard deviation of 0.2 Å. We characterize the conformational relaxation by calculating an enthalpy barrier using x-ray structures of myoglobin in both the MbCO photoproduct and deoxy conformations, and we find a small difference, ∼ 5 kJ/mol, between the two conformations. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 6864-6874 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The oxidation of carbon monoxide on a Pt(111) electrode surface is studied under transient and stationary reaction conditions in a 0.1 M HClO4 aqueous solution as a function of the applied electrode potential. The optical response is investigated by optical second harmonic generation (SHG) at 280 nm and infrared absorption spectroscopy (IRAS) starting at low potentials where the electrode is not reactive [e.g., 0.1 V vs the reversible hydrogen electrode (RHE)] towards more positive potentials where CO oxidation is initiated. For transient reaction conditions, in the absence of CO dissolved in solution, the oxidation starts at about 0.5 V vs. RHE and consists of a fast oxidation of about 10% of the adlayer and of a second reaction with slower kinetics involving the removal of the complete CO layer (overlayer stripping). Under steady-state conditions in CO-saturated solution the CO adlayer is stable up to 0.9 V vs RHE. At 0.63 V an overlayer phase transition is indicated by a 20% increase of the isotropic component of the second harmonic (SH) intensity (pp-polarization). The same potential region for this phase transition in the adlayer structure is derived from IRAS spectra after correcting for the effect of the thin layer electrolyte in IRAS measurements. The disappearance of hollow sites, the appearance of bridge sites, as well as an increased occupation of on-top sites at 0.63 V is interpreted as corresponding to the adlayer phase transition. The observations are consistent with a transition from the c(2×2) to the ((square root of)19×(square root of)19) adlayer structure of CO. The high sensitivity of SHG with regard to structural phase transitions of the CO adlayer is explained by distinct charge transfer contributions to the second-order surface susceptibility at different coordination sites. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 6875-6881 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Transport diffusion of argon in the unidirectional channels of the molecular sieve AlPO4-5 has been studied using molecular dynamics simulations. Using the Green–Kubo formalism, this nonequilibrium property is, for the first time, extracted from just one equilibrium simulation. Apart from the computational advantages above nonequilibrium simulations, the new method also provides a way to check the validity of the assumption of linear response, which is at the basis of both methods. The transport diffusion coefficient for argon at 87 K and half the maximum loading is found to be equal to Dt=(1.4±0.1)×10−5 cm2/s, of which approximately 20% can be attributed to correlated, collective motion. © 2000 American Institute of Physics.
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    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 5138-5140 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The energies of six stationary points on the OH+CO→HOCO→H+CO2 potential energy surface have been calculated using the G3 and CBS-QB3 methods. An analysis combining ab initio and experimental enthalpies yielded ΔHf298 K (trans-HOCO)=−42.9±1.5 kcal mol−1 (−43.8±1.4 kcal mol−1) at the G3(CBS-QB3) level of theory. These results confirm the revised HOCO heat of formation derived from photoionization spectroscopy and suggest that the HOCO potential well is 8.8 kcal mol−1 shallower than previously thought. We discuss the implications of these results for accurate Rice–Ramsperger–Kassel–Marcus modeling or quantum mechanical scattering calculations of the OH+CO reaction. © 2000 American Institute of Physics.
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  • 91
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    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 5141-5144 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We characterize the low-temperature dynamics of CO intercalated in C60 using NMR spectroscopy. CO in C60 is found to be dynamically inhomogeneous below 30 K: The 13CO line shapes reflect a dynamic disorder to static disorder transition, with only quantum tunneling among equivalent orientations in a local S6 symmetry potential remaining. The increased hindrance of the CO motion cannot be reconciled with common expectations of a homogeneous, thermally activated jumplike reorientation process, but is well accounted for in a model of orientational pinning due to asymmetric distortions of the cage potential. © 2000 American Institute of Physics.
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  • 92
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    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 5145-5153 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A new formula, EL−E∝(L+3/4)−3, to extrapolate energies, EL (that arise when the basis set is truncated at a finite angular momentum quantum number, L) to the limit, E, is derived and applied to the computation of the pair potential of He. Large basis sets up to d-aug-cc-pV5Z and -6Z are used, and in addition, a new cc-pV7Z set is presented. The full-CI is approximated using the "multireference averaged coupled-pair functional" (MR-ACPF) with 121 references. The calculated molecular constants of He2 are in excellent agreement with those recently obtained with r12-MR-ACPF [R. J. Gdanitz, Mol. Phys. 96, 1423 (1999)], but they agree only fairly with the complete-CI estimate of van Mourik and Dunning [J. Chem. Phys. 111, 9248 (1999)]. The potential of Komasa [J. Chem. Phys. 110, 7909 (1999)] which has been calculated with the "exponentially correlated Gaussians" method does not give a bound state. The sensitivity of the molecular constants 〈R〉 and D0 to errors of the interaction potential at different distances is estimated by perturbing the potential by Gaussian functions. The region of 5(approximately-less-than)R/a0(approximately-less-than)9 is found to be most sensitive. From this analysis, doubts arise that recent calculations (including the present one) are accurate enough to allow the molecular constants to be determined to better than (approximate)10%. © 2000 American Institute of Physics.
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  • 93
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    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 5171-5178 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The centroid molecular dynamics technique is applied to the case of chloride–water clusters to estimate their finite temperature quantum vibrational structure. We employ the flexible RWK2 water potential [J. R. Reimers, R. O. Watts, and M. L. Klein, Chem. Phys. 64, 95 (1982)] and the parametrization of a chloride–water interaction potential of Dorsett, Watts and Xantheas [J. Phys. Chem. A 103, 3351 (1999)]. We then investigate the temperature-dependent vibrational structure (infrared spectra). We find that the centroid molecular dynamics technique is capable of recovering a majority of the red shift associated with hydrogen bonding. © 2000 American Institute of Physics.
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  • 94
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    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 5154-5161 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A new implementation of the approximate coupled cluster singles and doubles method CC2 is reported, which is suitable for large scale integral-direct calculations. It employs the resolution of the identity (RI) approximation for two-electron integrals to reduce the CPU time needed for calculation and I/O of these integrals. We use a partitioned form of the CC2 equations which eliminates the need to store double excitation cluster amplitudes. In combination with the RI approximation this formulation of the CC2 equations leads to a reduced scaling of memory and disk space requirements with the number of correlated electrons (n) and basis functions (N) to, respectively, O(N2) and O(nN2), compared to O(n2N2) in previous implementations. The reduced CPU, memory and disk space requirements make it possible to perform CC2 calculations with accurate basis sets on large molecules, which would not be accessible with conventional implementations of the CC2 method. We present an application to vertical excitation energies of alkenes C2nH2n+2, for n=1–12, and report results for the lowest lying dipole-allowed transitions for the TZVPP basis sets, which for n=12 contain 1108 basis functions. Comparison with conventional CC2 results for the smaller alkenes show that for CC2 ground state energies and for excitation energies of valence states, the error due to the RI approximation is negligible compared to the usual basis set error, if auxiliary basis sets are used, which have been optimized for MP2 energy calculations. © 2000 American Institute of Physics.
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  • 95
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    The Journal of Chemical Physics 113 (2000), S. 6943-6949 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Molecular dynamics simulation is performed for linear liquid crystal molecules using a four-site model. The model consists of four Lennard-Jones centers which are bonded together via central potentials in a shish-kebab shape. When the molecules are left under their own vapor pressure, they exhibit isotropic and smectic B phases with no intervening nematic phase. A wall consisting of frozen Lennard-Jones centers is shown to anchor the molecules and to widen the range of the smectic regime. This demonstrates that the model can be used for molecular dynamics studies on liquid crystals in various polymer matrices. © 2000 American Institute of Physics.
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  • 96
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    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 6933-6942 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We report a theoretical study of the adsorption behavior of water–methanol mixtures in slit activated carbon micropores. The adsorption isotherms are obtained for a pore of width 2 nm at a temperature of 298 K from grand canonical ensemble Monte Carlo simulations. The water molecules are modeled using the four point transferable intermolecular potential functions (TIP4P) and methanol by the optimized potentials for liquid simulations (OPLS). Carboxyl (COOH) groups are used as active sites on a structured carbon surface. The effect of the relative contributions from dispersion and hydrogen bonding interactions of adsorbates, and of the chemical activation of adsorbents on adsorption behavior is investigated. The adsorption of the mixture components in activated carbon pores occurs by continuous filling, without the sharp capillary condensation observed in graphite pores. Water is preferentially adsorbed over methanol in activated carbon pores for a wide range of pressures, except at lower pressures. The hydrophilic nature of activated carbon pores results in the complexation of both water and methanol molecules with the active sites on the surfaces, leading to bulklike water behavior over the entire pore width. Solvation forces are also calculated as a function of pore size. The negative values found for the solvation force for all pore sizes reflect the hydrophilic interactions of the mixtures with the activated carbon surfaces. © 2000 American Institute of Physics.
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  • 97
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    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 6957-6965 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: To examine the manner in which molecular dynamics of a polymerizing liquid (stoichiometric amounts of 4,4′-diaminodicyclohexylamine and diglycidyl ether of bisphenol-A) evolves during thermal cycling from its (molecular) vitreous state to its fully polymerized vitreous state, calorimetry, and dielectric spectrometry were performed simultaneously in real time. The half-width of the relaxation spectrum of the liquid was relatively narrow and became narrower on heating. This was followed by an increase in the characteristic relaxation time and the spectrum became broader as polymerization occurred and reached completion. The dc conductivity initially increased and then decreased. The faster dynamics of the Johari–Goldstein relaxation in the fully polymerized state evolved as polymerization reached completion and the temperature increased. The dielectric polarization associated with this relaxation had a broad spectrum, whose half-width increased with decrease in the temperature. Its relaxation rate followed the Arrhenius equation with an activation energy of 63.4 kJ/mol. The temperature dependence of the faster relaxation did not change with the change in the overall configurational entropy of the liquid, a feature that substantiates the dynamic heterogeneity theories for the structure of the liquid and for the origin of the relaxation. © 2000 American Institute of Physics.
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  • 98
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    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 6950-6956 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: In theoretical work on the molecule, DNA is often treated, approximately, as a naturally straight, inextensible, isotropic elastic rod of circular cross section. It is shown that, consistent with this level of approximation, there exists a general connection between the free energy of supercoiling of plasmids formed by the DNA, and the writhe distribution in plasmids having a given value of the linking number difference, ΔLk. In particular, the writhe distribution in a collection of torsionally relaxed (ΔLk=0), but non-nicked, plasmids is completely determined once the free energy of supercoiling as a function of ΔLk is known. The writhe distribution in the supercoiled plasmids characterized by any other value of ΔLk, we shall also show, is simply related to the distribution in the relaxed plasmid, and, therefore, it, too, is completely determined. These general results are illustrated for two cases: Large plasmids for which the measured free energy of supercoiling, a quadratic function of ΔLk, implies a normal writhe distribution, and miniplasmids for which a theoretical expression for the free energy of supercoiling involving the frequencies of the normal modes of vibration of a circular elastic ring has recently become available. In this latter case, the writhe distribution for supercoiled plasmids is not normal, but shows a skewness related to a property of elastic rings, namely, the loss of stability of the circular equilibrium configuration of the rings when they are twisted beyond a critical value. Such a skewed writhe distribution for miniplasmids is, according to the model, associated with a free energy of supercoiling which is not, as has been assumed, a rigorously quadratic function of ΔLk. © 2000 American Institute of Physics.
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    The Journal of Chemical Physics 113 (2000), S. 5185-5192 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The theory is presented for asymptotically correcting the potentials of hybrid exchange-correlation functionals, i.e., those that include a fraction of orbital exchange. The Kohn–Sham equations involve a multiplicative potential due to the continuum part of the hybrid functional and a nonmultiplicative term due to the orbital exchange. In asymptotic regions the multiplicative σ-spin potential is corrected to take the form (CX−1)/r+εHOMO,σ+Iσ, where CX is the fraction of orbital exchange; εHOMO,σ is the σ-spin self-consistent highest occupied Kohn–Sham eigenvalue; and Iσ is an approximate ionization energy. For the hydrogen atom, the asymptotic correction leads to a potential that closely resembles the exact potential; the eigenvalue spectrum is intermediate between the Schrödinger and Hartree–Fock eigenvalues, reflecting the presence of orbital exchange. Kohn–Sham orbitals and eigenvalues determined from this procedure have been used to calculate singlet vertical excitation energies for CO, N2, H2CO, C2H4, and C6H6. The correction significantly improves excitation energies to Rydberg states, with mean absolute errors below 0.2 eV. However, despite including orbital exchange, the results do not represent an improvement over the results obtained by asymptotically correcting a recently developed GGA functional. The asymptotic correction is also shown to reduce static isotropic polarizabilities. © 2000 American Institute of Physics.
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    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 5214-5227 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The Fourier Grid Hamiltonian Multiconfigurational Self-Consistent-Field (FGH-MCSCF) method for calculating vibrational wavefunctions is presented. This method is designed to calculate multidimensional hydrogen nuclear wavefunctions for use in mixed quantum/classical molecular dynamics simulations of hydrogen transfer reactions. The FGH-MCSCF approach combines a MCSCF variational method, which describes the vibrational wavefunctions as linear combinations of configurations that are products of one-dimensional wavefunctions, with a Fourier grid method that represents the one-dimensional wavefunctions directly on a grid. In this method a full configuration interaction calculation is carried out in a truncated one-dimensional wavefunction space [analogous to complete active space self-consistent-field (CASSCF) in electronic structure theory]. A state-averaged approach is implemented to obtain a set of orthogonal multidimensional vibrational wavefunctions. The advantages of the FGH-MCSCF method are that it eliminates the costly calculation of multidimensional integrals, treats the entire range of the hydrogen coordinates without bias, avoids the expensive diagonalization of large matrices, and accurately describes ground and excited state hydrogen vibrational wavefunctions. This paper presents the derivation of the FGH-MCSCF method, as well as a series of test calculations on systems comparing its performance with exact diagonalization schemes. © 2000 American Institute of Physics.
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