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  • American Physical Society  (663,490)
  • American Institute of Physics (AIP)  (241,959)
  • Public Library of Science (PLoS)
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Publisher
Years
  • 1
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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: 1.1994 –
    Publisher: American Institute of Physics (AIP)
    Print ISSN: 1070-664X
    Electronic ISSN: 1089-7674
    Topics: Physics
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  • 3
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    Public Library of Science (PLoS)
    Online: 1.2005 –
    Publisher: Public Library of Science (PLoS)
    Print ISSN: 1553-734X
    Electronic ISSN: 1553-7358
    Topics: Biology , Computer Science
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  • 4
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    Public Library of Science (PLoS) | PubMed Central
    Online: 1.2009 – 10.2018
    Publisher: Public Library of Science (PLoS) , PubMed Central
    Electronic ISSN: 2157-3999
    Topics: Medicine , Natural Sciences in General
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  • 5
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    Public Library of Science (PLoS)
    Online: 1.2005 –
    Publisher: Public Library of Science (PLoS)
    Print ISSN: 1553-7390
    Electronic ISSN: 1553-7404
    Topics: Biology
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  • 6
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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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  • 7
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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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  • 8
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    American Physical Society
    Online: 1(1).1964 – 4(1).1968
    Publisher: American Physical Society
    Topics: Physics
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  • 9
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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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  • 10
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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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  • 11
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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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  • 12
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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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  • 13
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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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  • 14
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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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  • 15
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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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  • 16
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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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  • 17
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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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  • 18
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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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  • 19
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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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  • 20
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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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  • 21
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    Public Library of Science (PLoS)
    Online: 1.2003 –
    Publisher: Public Library of Science (PLoS)
    Print ISSN: 1544-9173
    Electronic ISSN: 1545-7885
    Topics: Biology
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  • 22
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    American Physical Society
    Online: 1993 –
    Publisher: American Physical Society
    Print ISSN: 0003-0503
    Topics: Physics
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  • 23
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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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  • 24
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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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  • 25
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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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  • 26
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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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  • 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: 1.2013 –
    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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  • 29
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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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  • 30
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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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  • 31
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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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  • 32
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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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  • 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
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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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  • 35
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    American Physical Society
    Online: 1995 –
    Publisher: American Physical Society
    Topics: Physics
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  • 36
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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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  • 37
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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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  • 38
    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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  • 39
    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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  • 40
    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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  • 41
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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
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  • 42
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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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  • 43
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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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  • 44
    Publication Date: 2022-05-25
    Description: © 2005 Sullivan et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. The definitive version was published in PLoS Biology 3 (2005): e144, doi:10.1371/journal.pbio.0030144.
    Description: The oceanic cyanobacteria Prochlorococcus are globally important, ecologically diverse primary producers. It is thought that their viruses (phages) mediate population sizes and affect the evolutionary trajectories of their hosts. Here we present an analysis of genomes from three Prochlorococcus phages: a podovirus and two myoviruses. The morphology, overall genome features, and gene content of these phages suggest that they are quite similar to T7-like (P-SSP7) and T4-like (P-SSM2 and P-SSM4) phages. Using the existing phage taxonomic framework as a guideline, we examined genome sequences to establish ‘‘core’’ genes for each phage group. We found the podovirus contained 15 of 26 core T7-like genes and the two myoviruses contained 43 and 42 of 75 core T4-like genes. In addition to these core genes, each genome contains a significant number of ‘‘cyanobacterial’’ genes, i.e., genes with significant best BLAST hits to genes found in cyanobacteria. Some of these, we speculate, represent ‘‘signature’’ cyanophage genes. For example, all three phage genomes contain photosynthetic genes (psbA, hliP) that are thought to help maintain host photosynthetic activity during infection, as well as an aldolase family gene (talC) that could facilitate alternative routes of carbon metabolism during infection. The podovirus genome also contains an integrase gene (int) and other features that suggest it is capable of integrating into its host. If indeed it is, this would be unprecedented among cultured T7-like phages or marine cyanophages and would have significant evolutionary and ecological implications for phage and host. Further, both myoviruses contain phosphate-inducible genes (phoH and pstS) that are likely to be important for phage and host responses to phosphate stress, a commonly limiting nutrient in marine systems. Thus, these marine cyanophages appear to be variations of two well-known phages—T7 and T4—but contain genes that, if functional, reflect adaptations for infection of photosynthetic hosts in low-nutrient oceanic environments.
    Description: This research was supported by the US DOE under grant numbers DEFG02– 99ER62814 and DE-FG02–02ER63445, and the National Science Foundation under grant number OCE-9820035 (to SWC).
    Keywords: Oceanic cyanobacteria ; Prochlorococcus phages
    Repository Name: Woods Hole Open Access Server
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  • 45
    Publication Date: 2022-05-25
    Description: © 2006 Bordenstein et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. The definitive version was published in PLoS Pathogens 2(2006): e43, doi:10.1371/journal.ppat.0020043.
    Description: By manipulating arthropod reproduction worldwide, the heritable endosymbiont Wolbachia has spread to pandemic levels. Little is known about the microbial basis of cytoplasmic incompatibility (CI) except that bacterial densities and percentages of infected sperm cysts associate with incompatibility strength. The recent discovery of a temperate bacteriophage (WO-B) of Wolbachia containing ankyrin-encoding genes and virulence factors has led to intensifying debate that bacteriophage WO-B induces CI. However, current hypotheses have not considered the separate roles that lytic and lysogenic phage might have on bacterial fitness and phenotype. Here we describe a set of quantitative approaches to characterize phage densities and its associations with bacterial densities and CI. We enumerated genome copy number of phage WO-B and Wolbachia and CI penetrance in supergroup A- and B-infected males of the parasitoid wasp Nasonia vitripennis. We report several findings: (1) variability in CI strength for A-infected males is positively associated with bacterial densities, as expected under the bacterial density model of CI, (2) phage and bacterial densities have a significant inverse association, as expected for an active lytic infection, and (3) CI strength and phage densities are inversely related in A-infected males; similarly, males expressing incomplete CI have significantly higher phage densities than males expressing complete CI. Ultrastructural analyses indicate that approximately 12% of the A Wolbachia have phage particles, and aggregations of these particles can putatively occur outside the Wolbachia cell. Physical interactions were observed between approximately 16% of the Wolbachia cells and spermatid tails. The results support a low to moderate frequency of lytic development in Wolbachia and an overall negative density relationship between bacteriophage and Wolbachia. The findings motivate a novel phage density model of CI in which lytic phage repress Wolbachia densities and therefore reproductive parasitism. We conclude that phage, Wolbachia, and arthropods form a tripartite symbiotic association in which all three are integral to understanding the biology of this widespread endosymbiosis. Clarifying the roles of lytic and lysogenic phage development in Wolbachia biology will effectively structure inquiries into this research topic.
    Description: This work was supported by grants from the NASA Astrobiology Institute (NNA04CC04A) and National Institutes of Health (R01 GM62626-01) to JJW, and by the Marine Biological Laboratory's Program in Global Infectious Diseases, funded by the Ellison Medical Foundation, to SRB.
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  • 46
    Publication Date: 2022-05-25
    Description: © 2006 Parfrey et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. The definitive version was published in PLoS Genetics 2 (2006): e220, doi:10.1371/journal.pgen.0020220.
    Description: Perspectives on the classification of eukaryotic diversity have changed rapidly in recent years, as the four eukaryotic groups within the five-kingdom classification—plants, animals, fungi, and protists—have been transformed through numerous permutations into the current system of six ‘‘supergroups.’’ The intent of the supergroup classification system is to unite microbial and macroscopic eukaryotes based on phylogenetic inference. This supergroup approach is increasing in popularity in the literature and is appearing in introductory biology textbooks. We evaluate the stability and support for the current six-supergroup classification of eukaryotes based on molecular genealogies. We assess three aspects of each supergroup: (1) the stability of its taxonomy, (2) the support for monophyly (single evolutionary origin) in molecular analyses targeting a supergroup, and (3) the support for monophyly when a supergroup is included as an out-group in phylogenetic studies targeting other taxa. Our analysis demonstrates that supergroup taxonomies are unstable and that support for groups varies tremendously, indicating that the current classification scheme of eukaryotes is likely premature. We highlight several trends contributing to the instability and discuss the requirements for establishing robust clades within the eukaryotic tree of life.
    Description: This work is supported by the National Science Foundation Assembling the Tree of Life grant (043115) to DB, DJP, and LAK.
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  • 47
    Publication Date: 2022-05-25
    Description: This is an open-access article distributed under the terms of the Creative Commons Public Domain dedication. The definitive version was published in PLoS Biology 4 (2006): e383, doi:10.1371/journal.pbio.0040383.
    Description: Presented here is the complete genome sequence of Thiomicrospira crunogena XCL-2, representative of ubiquitous chemolithoautotrophic sulfur-oxidizing bacteria isolated from deep-sea hydrothermal vents. This gammaproteobacterium has a single chromosome (2,427,734 base pairs), and its genome illustrates many of the adaptations that have enabled it to thrive at vents globally. It has 14 methyl-accepting chemotaxis protein genes, including four that may assist in positioning it in the redoxcline. A relative abundance of coding sequences (CDSs) encoding regulatory proteins likely control the expression of genes encoding carboxysomes, multiple dissolved inorganic nitrogen and phosphate transporters, as well as a phosphonate operon, which provide this species with a variety of options for acquiring these substrates from the environment. Thiom. crunogena XCL-2 is unusual among obligate sulfur-oxidizing bacteria in relying on the Sox system for the oxidation of reduced sulfur compounds. The genome has characteristics consistent with an obligately chemolithoautotrophic lifestyle, including few transporters predicted to have organic allocrits, and Calvin-Benson-Bassham cycle CDSs scattered throughout the genome.
    Description: This work was performed under the auspices of the United States Department of Energy by Lawrence Livermore National Laboratory, University of California, under contract W-7405-ENG-48. Genome closure was funded in part by a University of South Florida Innovative Teaching Grant (to KMS). KMS, SKF, and CAK gratefully acknowledge support from the United States Department of Agriculture Higher Education Challenge Grants Program (Award # 20053841115876). SMS kindly acknowledges support through a fellowship received from the Hanse Wissenschaftskolleg in Delmenhorst, Germany (http://www.h-w-k.de). MH was supported by a Woods Hole Oceanographic Institution postdoctoral scholarship.
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  • 48
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    Publication Date: 2022-05-25
    Description: © 2004 Jennifer J. Wernegreen. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. The definitive version was published in PLoS Biology 2 (2004): e68, doi:10.1371/journal.pbio.0020068.
    Description: Symbiosis, an interdependent relationship between two species, is an important driver of evolutionary novelty and ecological diversity. Microbial symbionts in particular have been major evolutionary catalysts throughout the 4 billion years of life on earth and have largely shaped the evolution of complex organisms. Endosymbiosis is a specifi c type of symbiosis in which one—typically microbial—partner lives within its host and represents the most intimate contact between interacting organisms. Mitochondria and chloroplasts, for example, result from endosymbiotic events of lasting significance that extended the range of acceptable habitats for life. The wide distribution of intracellular bacteria across diverse hosts and marine and terrestrial habitats testifies to the continued importance of endosymbiosis in evolution. Among multicellular organisms, insects as a group form exceptionally diverse associations with microbial associates, including bacteria that live exclusively within host cells and undergo maternal transmission to offspring. These microbes have piqued the interest of evolutionary biologists because they represent a wide spectrum of evolutionary strategies, ranging from obligate mutualism to reproductive parasitism (Buchner 1965; Ishikawa 2003) (Box 1; Table 1).
    Description: JJW gratefully acknowledges the support of the National Institutes of Health (R01 GM62626-01), the National Science Foundation (DEB 0089455), the National Aeronautics and Space Administration Astrobiology Institute (NNA04CC04A), and the Josephine Bay Paul and C. Michael Paul Foundation.
    Keywords: Endosymbiosis ; Endosymbiosis manipulation
    Repository Name: Woods Hole Open Access Server
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  • 49
    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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  • 50
    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.
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  • 51
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    In:  EPIC3PLOS ONE, Public Library of Science (PLoS), 15(8), pp. e0237704-e0237704, ISSN: 1932-6203
    Publication Date: 2023-06-21
    Description: Since plastics degrade very slowly, they remain in the environment on much longer timescales than most natural organic substrates and provide a novel habitat for colonization by bacterial communities. The spectrum of relationships between plastics and bacteria, however, is little understood. The first objective of this study was to examine plastics as substrates for communities of Bacteria in estuarine surface waters. We used next-generation sequencing of the 16S rRNA gene to characterize communities from plastics collected in the field, and over the course of two colonization experiments, from biofilms that developed on plastic (low-density polyethylene, high-density polyethylene, polypropylene, polycarbonate, polystyrene) and glass substrates placed in the environment. Both field sampling and colonization experiments were conducted in estuarine tributaries of the lower Chesapeake Bay. As a second objective, we concomitantly analyzed biofilms on plastic substrates to ascertain the presence and abundance of Vibrio spp. bacteria, then isolated three human pathogens, V. cholerae, V. parahaemolyticus, and V. vulnificus, and determined their antibiotic-resistant profiles. In both components of this study, we compared our results with analyses conducted on paired samples of estuarine water. This research adds to a nascent literature that suggests environmental factors govern the development of bacterial communities on plastics, more so than the characteristics of the plastic substrates themselves. In addition, this study is the first to culture three pathogenic vibrios from plastics in estuaries, reinforcing and expanding upon earlier reports of plastic pollution as a habitat for Vibrio species. The antibiotic resistance detected among the isolates, coupled with the longevity of plastics in the aqueous environment, suggests biofilms on plastics have potential to persist and serve as focal points of potential pathogens and horizontal gene transfer.
    Repository Name: EPIC Alfred Wegener Institut
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  • 52
    Publication Date: 2023-06-21
    Description: Multiomics approaches need to be applied in the central Arctic Ocean to benchmark biodiversity change and to identify novel species and their genes. As part of MOSAiC, EcoOmics will therefore be essential for conservation and sustainable bioprospecting in one of the least explored ecosystems on Earth.
    Repository Name: EPIC Alfred Wegener Institut
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  • 53
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    In:  PLoS ONE vol. 9 no. 12, pp. e115750-e115750
    Publication Date: 2024-01-12
    Keywords: Multidisciplinary
    Repository Name: National Museum of Natural History, Netherlands
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  • 54
    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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  • 55
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    Public Library of Science (PLoS)
    In:  EPIC3PLOS ONE, Public Library of Science (PLoS), 18(8), pp. e0290437-e0290437, ISSN: 1932-6203
    Publication Date: 2023-08-31
    Description: Due to its involvement in numerous feedbacks, sea ice plays a crucial role not only for polar climate but also at global scale. We analyse state-of-the-art observed, reconstructed, and modelled sea-ice concentration (SIC) together with sea surface temperature (SST) to disentangle the influence of different forcing factors on the variability of these coupled fields. Canonical Correlation Analysis provides distinct pairs of coupled Arctic SIC–Atlantic SST variability which are linked to prominent oceanic and atmospheric modes of variability over the period 1854–2017. The first pair captures the behaviour of the Atlantic meridional overturning circulation (AMOC) while the third and can be associated with the North Atlantic Oscillation (NAO) in a physically consistent manner. The dominant global SIC–Atlantic SST coupled mode highlights the contrast between the responses of Arctic and Antarctic sea ice to changes in AMOC over the 1959–2021 period. Model results indicate that coupled SST–SIC patterns can be associated with changes in ocean circulation. We conclude that a correct representation of AMOC-induced coupled SST–SIC variability in climate models is essential to understand the past, present and future sea-ice evolution.
    Repository Name: EPIC Alfred Wegener Institut
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  • 56
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    In:  EPIC3PLOS ONE, Public Library of Science (PLoS), 17(9), pp. e0273623-e0273623, ISSN: 1932-6203
    Publication Date: 2023-10-23
    Description: While the output of a team is evident, the productivity of each team member is typically not readily identifiable. In this paper we consider the problem of measuring the productivity of team members. We propose a new concept of coworker productivity, which we refer to as eigenvalue productivity (EVP). We demonstrate the existence and uniqueness of our concept and show that it possesses several desirable properties. Also, we suggest a procedure for specifying the required productivity matrix of a team, and illustrate the operational practicability of EVP by means of three examples representing different types of available data.
    Repository Name: EPIC Alfred Wegener Institut
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  • 57
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    In:  EPIC3PLOS ONE, Public Library of Science (PLoS), 18(7), pp. e0286036-e0286036, ISSN: 1932-6203
    Publication Date: 2023-08-01
    Description: Euphausia superba is a key species of the Southern Ocean, impacted by climate change and human exploitation. Understanding how these changes affect the distribution and abundance of krill is crucial for generating projections of change for Southern Ocean ecosystems. Krill growth is an important indicator of habitat suitability and a series of models have been developed and used to examine krill growth potential at different spatial and temporal scales. The available models have been developed using a range of empirical and mechanistic approaches, providing alternative perspectives and comparative analyses of the key processes influencing krill growth. Here we undertake an intercomparison of a suite of the available models to understand their sensitivities to major driving variables. This illustrates that the results are strongly determined by the model structure and technical characteristics, and the data on which they were developed and validated. Our results emphasize the importance of assessing the constraints and requirements of individual krill growth models to ensure their appropriate application. The study also demonstrates the value of the development of alternative modelling approaches to identify key processes affecting the dynamics of krill. Of critical importance for modelling the growth of krill is appropriately assessing and accounting for differences in estimates of food availability resulting from alternative methods of observation. We suggest that an intercomparison approach is particularly valuable in the development and application of models for the assessment of krill growth potential at circumpolar scales and for future projections. As another result of the intercomparison, the implementations of the models used in this study are now publicly available for future use and analyses.
    Repository Name: EPIC Alfred Wegener Institut
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  • 58
    Publication Date: 2024-02-07
    Description: Phylogeographic patterns and sex-biased dispersal were studied in riverine populations of West Indian (Trichechus manatus) and Amazonian manatees (T. inunguis) in South America, using 410bp D-loop (Control Region, Mitochondrial DNA) sequences and 15 nuclear microsatellite loci. This multi-locus approach was key to disentangle complex patterns of gene flow among populations. D-loop analyses revealed population structuring among all Colombian rivers for T. manatus, while microsatellite data suggested no structure. Two main populations of T. inunguis separating the Colombian and Peruvian Amazon were supported by analysis of the D-loop and microsatellite data. Overall, we provide molecular evidence for differences in dispersal patterns between sexes, demonstrating male-biased gene flow dispersal in riverine manatees. These results are in contrast with previously reported levels of population structure shown by microsatellite data in marine manatee populations, revealing low habitat restrictions to gene flow in riverine habitats, and more significant dispersal limitations for males in marine environments. © 2012 Satizábal et al.
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  • 59
    Publication Date: 2024-02-28
    Description: The superfamily Orthalicoidea comprises approximately 2,000 species of terrestrial gastropods, mostly concentrated in the Neotropics but also present in southern Africa and Oceania. We provide a multi-marker molecular phylogeny of this superfamily, reassessing its \nfamily- and genus-level classification. We exclude two families from the group, Odontostomidae and Vidaliellidae, transferring them to Rhytidoidea based on their phylogenetic relationships as recovered herein. Two new families are recognized herein as members of \nOrthalicoidea, Tomogeridae and Cyclodontinidae fam. nov. The family Megaspiridae and \nthe subfamily Prestonellinae are paraphyletic but are retained herein for taxonomic stability. \nThe subfamily Placostylinae is synonymized with Bothriembryontinae. The new genera \nAlterorhinus gen. nov. and Sanniostracus gen. nov. containing some Brazilian species are \ndescribed here to better reflect the phylogeny. The fossil record and paleobiogeographic \nhistory of the group is explored under the new phylogenetic framework.
    Repository Name: National Museum of Natural History, Netherlands
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  • 60
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    In:  PLOS Computational Biology vol. 19 no. 10, pp. e1011541-e1011541
    Publication Date: 2024-03-12
    Description: Insect population numbers and biodiversity have been rapidly declining with time, and monitoring \nthese trends has become increasingly important for conservation measures to be \neffectively implemented. But monitoring methods are often invasive, time and resource \nintense, and prone to various biases. Many insect species produce characteristic sounds \nthat can easily be detected and recorded without large cost or effort. Using deep learning \nmethods, insect sounds from field recordings could be automatically detected and classified \nto monitor biodiversity and species distribution ranges. We implement this using recently \npublished datasets of insect sounds (up to 66 species of Orthoptera and Cicadidae) and \nmachine learning methods and evaluate their potential for acoustic insect monitoring. We \ncompare the performance of the conventional spectrogram-based audio representation \nagainst LEAF, a new adaptive and waveform-based frontend. LEAF achieved better classification \nperformance than the mel-spectrogram frontend by adapting its feature extraction \nparameters during training. This result is encouraging for future implementations of deep \nlearning technology for automatic insect sound recognition, especially as larger datasets \nbecome available.
    Repository Name: National Museum of Natural History, Netherlands
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  • 61
    Publication Date: 2024-03-29
    Description: Ecological indicators for monitoring strategies are expected to combine three major characteristics: ecological significance, statistical credibility, and cost-effectiveness. Strategies based on stranding networks rank highly in cost-effectiveness, but their ecological significance and statistical credibility are disputed. Our present goal is to improve the value of stranding data as population indicator as part of monitoring strategies by constructing the spatial and temporal null hypothesis for strandings. The null hypothesis is defined as: small cetacean distribution and mortality are uniform in space and constant in time. We used a drift model to map stranding probabilities and predict stranding patterns of cetacean carcasses under H0 across the North Sea, the Channel and the Bay of Biscay, for the period 1990–2009. As the most common cetacean occurring in this area, we chose the harbour porpoise Phocoena phocoena for our modelling. The difference between these strandings expected under H0 and observed strandings is defined as the stranding anomaly. It constituted the stranding data series corrected for drift conditions. Seasonal decomposition of stranding anomaly suggested that drift conditions did not explain observed seasonal variations of porpoise strandings. Long-term stranding anomalies increased first in the southern North Sea, the Channel and Bay of Biscay coasts, and finally the eastern North Sea. The hypothesis of changes in porpoise distribution was consistent with local visual surveys, mostly SCANS surveys (1994 and 2005). This new indicator could be applied to cetacean populations across the world and more widely to marine megafauna.
    Repository Name: National Museum of Natural History, Netherlands
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  • 62
    Publication Date: 2024-04-09
    Description: Biodiversity loss is a major global challenge and minimizing extinction rates is the goal of several multilateral environmental agreements. Policy decisions require comprehensive, spatially explicit information on species’ distributions and threats. We present an analysis of the conservation status of 14,669 European terrestrial, freshwater and marine species (ca. 10% of the continental fauna and flora), including all vertebrates and selected groups of invertebrates and plants. Our results reveal that 19% of European species are threatened with extinction, with higher extinction risks for plants (27%) and invertebrates (24%) compared to vertebrates (18%). These numbers exceed recent IPBES (Intergovernmental Platform on Biodiversity and Ecosystem Services) assumptions of extinction risk. Changes in agricultural practices and associated habitat loss, overharvesting, pollution and development are major threats to biodiversity. Maintaining and restoring sustainable land and water use practices is crucial to minimize future biodiversity declines.
    Repository Name: National Museum of Natural History, Netherlands
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  • 63
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    In:  EPIC3PLOS Climate, Public Library of Science (PLoS), 3(3), pp. e0000360-e0000360, ISSN: 2767-3200
    Publication Date: 2024-04-29
    Repository Name: EPIC Alfred Wegener Institut
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  • 64
    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
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 65
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    In:  EPIC3PLOS ONE, Public Library of Science (PLoS), 19(4), pp. e0300138-e0300138, ISSN: 1932-6203
    Publication Date: 2024-04-26
    Description: Using the climate model CLIMBER-X, we present an efficient method for assimilating the temporal evolution of surface temperatures for the last deglaciation covering the period 22000 to 6500 years before the present. The data assimilation methodology combines the data and the underlying dynamical principles governing the climate system to provide a state estimate of the system, which is better than that which could be obtained using just the data or the model alone. In applying an ensemble Kalman filter approach, we make use of the advances in the parallel data assimilation framework (PDAF), which provides parallel data assimilation functionality with a relatively small increase in computation time. We find that the data assimilation solution depends strongly on the background evolution of the decaying ice sheets rather than the assimilated temperatures. Two different ice sheet reconstructions result in a different deglacial meltwater history, affecting the large-scale ocean circulation and, consequently, the surface temperature. We find that the influence of data assimilation is more pronounced on regional scales than on the global mean. In particular, data assimilation has a stronger effect during millennial warming and cooling phases, such as the Bølling-Allerød and Younger Dryas, especially at high latitudes with heterogeneous temperature patterns. Our approach is a step toward a comprehensive paleo-reanalysis on multi-millennial time scales, including incorporating available paleoclimate data and accounting for their uncertainties in representing regional climates.
    Repository Name: EPIC Alfred Wegener Institut
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  • 66
    Publication Date: 2024-05-09
    Description: The circadian clock controls behavior and metabolism in various organisms. However, the exact timing and strength of rhythmic phenotypes can vary significantly between individuals of the same species. This is highly relevant for rhythmically complex marine environments where organismal rhythmic diversity likely permits the occupation of different microenvironments. When investigating circadian locomotor behavior of Platynereis dumerilii, a model system for marine molecular chronobiology, we found strain-specific, high variability between individual worms. The individual patterns were maintained for several weeks. A diel head transcriptome comparison of behaviorally rhythmic versus arrhythmic wild-type worms showed that 24-h cycling of core circadian clock transcripts is identical between both behavioral phenotypes. While behaviorally arrhythmic worms showed a similar total number of cycling transcripts compared to their behaviorally rhythmic counterparts, the annotation categories of their transcripts, however, differed substantially. Consistent with their locomotor phenotype, behaviorally rhythmic worms exhibit an enrichment of cycling transcripts related to neuronal/behavioral processes. In contrast, behaviorally arrhythmic worms showed significantly increased diel cycling for metabolism- and physiology-related transcripts. The prominent role of the neuropeptide pigment-dispersing factor (PDF) in Drosophila circadian behavior prompted us to test for a possible functional involvement of Platynereis pdf. Differing from its role in Drosophila, loss of pdf impacts overall activity levels but shows only indirect effects on rhythmicity. Our results show that individuals arrhythmic in a given process can show increased rhythmicity in others. Across the Platynereis population, rhythmic phenotypes exist as a continuum, with no distinct “boundaries” between rhythmicity and arrhythmicity. We suggest that such diel rhythm breadth is an important biodiversity resource enabling the species to quickly adapt to heterogeneous or changing marine environments. In times of massive sequencing, our work also emphasizes the importance of time series and functional tests.
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  • 67
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    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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  • 68
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    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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  • 69
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    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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  • 70
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    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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  • 71
    Electronic Resource
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    College Park, Md. : American Institute of Physics (AIP)
    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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    The Journal of Chemical Physics 113 (2000), S. 7571-7577 
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    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 
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    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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    The Journal of Chemical Physics 113 (2000), S. 7564-7570 
    ISSN: 1089-7690
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    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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    The Journal of Chemical Physics 113 (2000), S. 7530-7545 
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    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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    The Journal of Chemical Physics 113 (2000), S. 7578-7581 
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    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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    The Journal of Chemical Physics 113 (2000), S. 7588-7592 
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    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 
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    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 
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    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 
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    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 
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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 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 
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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 
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    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 
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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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    Source: AIP Digital Archive
    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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  • 96
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    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 6788-6794 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    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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  • 97
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    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 6815-6821 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    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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  • 98
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    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 6795-6802 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    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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  • 99
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 6803-6814 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    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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  • 100
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 6822-6830 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    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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