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  • Springer  (134)
  • Copernicus  (21)
  • American Institute of Physics (AIP)  (18)
  • American Meteorological Society (AMS)
  • 2010-2014  (67)
  • 1995-1999  (67)
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  • 1935-1939  (14)
  • 1920-1924  (18)
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  • 11
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 103 (1995), S. 2888-2902 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A semiclassical time-dependent self-consistent-field (TDSCF) formulation is developed for the description of internal conversion (IC) processes in polyatomic molecules. The total density operator is approximated by a semiclassical ansatz, which couples the electronic degrees of freedom to the nuclear degrees of freedom in a self-consistent manner, whereby the vibrational density operator is described in terms of Gaussian wave packets. The resulting TDSCF formulation represents a generalization of familiar classical-path theories, and is particularly useful to make contact to quantum-mechanical formulations. To avoid problems associated with spurious phase factors, we assume rapid randomization of the nuclear phases and a single vibrational density operator for all electronic states. Classically, the latter approximation corresponds to a single trajectory propagating along a "mean path'' instead of several state-specific trajectories, which may become a critical assumption for the description of IC processes. The validity and the limitations of the mean-path approximation are discussed in detail, including both theoretical as well as numerical studies. It is shown that for constant diabatic coupling elements Vkk′ the mean-path approximation should be appropriate in many cases, whereas in the case of coordinate-dependent coupling Vkk′(x) the approximation is found to lead to an underestimation of the overall relaxation rate.As a remedy for this inadequacy of the mean-path approximation, we employ dynamical corrections to the off-diagonal elements of the electronic density operator, as has been suggested by Meyer and Miller [J. Chem. Phys. 70, 3214 (1979)]. We present detailed numerical studies, adopting (i) a two-state three-mode model of the S1−S2 conical intersection in pyrazine, and (ii) a three-state five-mode and a five-state sixteen-mode model of the C˜→B˜→X˜ IC process in the benzene cation. The comparison with exact basis-set calculations for the two smaller model systems and the possible predictions for larger systems demonstrate the capability of the semiclassical model for the description of ultrafast IC processes. © 1995 American Institute of Physics.
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  • 12
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 65-76 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Necessary conditions under which a classical description will give the correct quantum relaxation behavior are analyzed. Assuming a nonequilibrium preparation, it is shown that the long-time mean values of observables can be expressed in terms of the spectral density and state-specific level densities of the system. Any approximation that reproduces these quantities therefore yields the correct expectation values at long times. Apart from this rigorous condition, a weaker but more practical criterion is established, that is, to require that the total level density is well approximated in the energy range defined by the spectral density. Since the integral level density is directly proportional to the phase-space volume that is energetically accessible to the system, the latter condition means that an appropriate classical approximation should explore the same phase-space volume as the quantum description. In general, however, this is not the case. A well-known example is the unrestricted flow of zero-point energy in classical mechanics. To correct for this flaw of classical mechanics, quantum corrections are derived which result in a restriction of the classically accessible phase space. At the simplest level of the theory, these corrections are shown to correspond to the inclusion of only a fraction of the full zero-point energy into the classical calculation. Based on these considerations, a general strategy for the classical simulation of quantum relaxation dynamics is suggested. The method is (i) dynamically consistent in that it refers to the behavior of the ensemble rather than to the behavior of individual trajectories, (ii) systematic in that it provides (rigorous as well as minimal) criteria which can be checked in a practical calculation, and (iii) practical in that it retains the conceptional and computational simplicity of a standard quasiclassical calculation. Employing various model problems which allow for an analytical evaluation of the quantities of interest, the virtues and limitations of the approach are discussed. © 1999 American Institute of Physics.
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  • 13
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 77-88 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The unphysical flow of zero-point energy (ZPE) in classical trajectory calculations is a consequence of the fact that the classical phase-space distribution may enter regions of phase space that correspond to a violation of the uncertainty principle. To restrict the classically accessible phase space, we employ a reduced ZPE γεZP, whereby the quantum correction γ accounts for the fraction of ZPE included. This ansatz is based on the theoretical framework given in Paper I [G. Stock and U. Müller, J. Chem. Phys. 111, 65 (1999), preceding paper], which provides a general connection between the level density of a system and its relaxation behavior. In particular, the theory establishes various criteria which allows us to explicitly calculate the quantum correction γ. By construction, this strategy assures that the classical calculation attains the correct long-time values and, as a special case thereof, that the ZPE is treated properly. As a stringent test of this concept, a recently introduced classical description of nonadiabatic quantum dynamics is adopted [G. Stock and M. Thoss, Phys. Rev. Lett. 78, 578 (1997)], which facilitates a classical treatment of discrete quantum degrees of freedom through a mapping of discrete onto continuous variables. Resulting in negative population probabilities, the quasiclassical implementation of this theory significantly suffers from spurious flow of ZPE. Employing various molecular model systems including multimode models with conically intersecting potential-energy surfaces as well as several spin-boson-type models with an Ohmic bath, detailed numerical studies are presented. In particular, it is shown, that the ZPE problem indeed vanishes, if the quantum correction γ is chosen according to the criteria established in Paper I. Moreover, the complete time evolution of the classical simulations is found to be in good agreement with exact quantum-mechanical calculations. Based on these studies, the general applicability of the method, the performance of the classical description of nonadiabatic quantum dynamics, as well as various issues concerning classical and quantum ergodicity are discussed. © 1999 American Institute of Physics.
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  • 14
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 107 (1997), S. 6230-6245 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A mixed quantum-classical description of nonadiabatic photoreactions such as internal conversion and electron transfer is outlined. In particular the validity and limitations of Tully's surface-hopping (SH) model [J. Chem. Phys. 93, 1061 (1990)] is investigated in the case of photoinduced relaxation processes which are triggered by a multidimensional conical intersection (or avoided crossing) of two potential-energy surfaces. Detailed numerical studies are presented, adopting (i) a three-mode model of the S2→S1 internal-conversion process in pyrazine, (ii) a multimode model of ultrafast intramolecular electron-transfer, (iii) a model exhibiting nonadiabatic photoisomerization dynamics, and (iv) various spin-boson-type models with an Ohmic bath for the description of electron-transfer in solution. The SH simulations are compared to exact quantum-mechanical calculations as well as to results obtained by an alternative mixed quantum-classical description, that is, the self-consistent classical-path method. In all cases, the SH data are shown to reproduce the quantum results at least qualitatively; in some cases the SH results are in quantitative agreement with the complex electronic and vibrational relaxation dynamics exhibited by the quantum calculations. Depending on the physical situation under consideration, either the SH or the self-consistent classical-path method was found to be superior. The characteristic features of a mixed quantum-classical description of photoinduced bound-state dynamics (e.g., the start of the trajectories on a diabatic electronic potential-energy surface, high chance of a trajectory undergoing multiple electronic transitions) as well as the specific problems of the SH approach are discussed in some detail. In particular, the focus is on the ability of a method to account for the branching of trajectories, to correctly describe the electronic phase coherence and the vibrational motion on coupled potential-energy surfaces, and to obey the principle of microreversibility. Furthermore, an alternative way to handle classically forbidden electronic transitions is proposed, which is shown to lead to significantly better results than the usual procedure. © 1997 American Institute of Physics.
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  • 15
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 108 (1998), S. 7516-7526 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A mixed quantum-classical formulation of nonadiabatic molecular processes is outlined. Based on a recently introduced mapping formalism [Stock and Thoss, Phys. Rev. Lett. 78, 578 (1997)], the formulation employs a quantum-mechanically exact mapping of discrete electronic states onto continuous variables, thus describing the dynamics of both electronic and nuclear degrees of freedom by continuous variables. It is shown that the classical evaluation of the mapping formalism results in a self-consistent description of electronic and nuclear degrees of freedom, which treats both types of dynamical variables in a completely equivalent way. The applicability of the approach is thus solely determined by the validity of the classical approximation and does not rest on additional assumptions such as the ad hoc combination of classical and quantum-mechanical theories. The observation of unrestricted flow of zero-point energy in the electronic degrees of freedom indicates the limits of the classical approximation. However, it is shown that this problem can virtually be removed by restricting the classically accessible phase-space. Adopting a multidimensional model of the internal-conversion process in the benzene cation, it is demonstrated that the classical mapping approach is able to account for the branching of classical trajectories in the presence of multiple surface crossings. The classical simulations are found to match the exact quantum-mechanical reference calculations quite accurately. The virtues and limitations of various mixed quantum-classical descriptions are discussed by comparing the mapping approach to the classical-path, the classical electron-analog, and the surface-hopping formulation, respectively. © 1998 American Institute of Physics.
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  • 16
    Electronic Resource
    Electronic Resource
    Springer
    Journal of ornithology 138 (1997), S. 387-411 
    ISSN: 1439-0361
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Description / Table of Contents: Zusammenfassung Der Einfluß von Störreizen auf das Energiebudget von Ringelgänsen wurde im Frühjahr 1991 in zwei Vorland-Salzwiesen des Nationalparks Schleswig-Holsteinisches Wattenmeer vergleichend untersucht. Die Häufigkeit störreizbedingter Reaktionen der Gänse (Störreizhäufigkeit) wurde als Index für die anthropogene Beeinflussung der Gebiete herangezogen. Die Beeinflussung war in Westerhever mit 1,5±0,7 Reaktionen/h signifikant größer als vor dem Norderheverkoog (1,0±0,6 Reaktionen/h). Mit zunehmender Aktivitätszeit wurde in beiden Gebieten im Verlauf des Frühjahres mehr umsetzbare Energie aufgenommen. In Westerhever haben die Gänse im Vergleich zu denen vor dem Norderheverkoog mit Ausnahme des Mai jeweils mehr umsetzbare Energie aufgenommen. Die energetischen Kosten (DEE) der Gänse wurden anhand der Zeit-Energie-Budget Methode und über die gemessene Körpermasseentwicklung von Fänglingen berechnet. Beide Methoden erzielten vergleichbare Ergebnisse; die Unterschiede betrugen je nach Gebiet 0,4 bis 4,5 %. In Westerhever verzeichneten die Gänse im Vergleich zu denen vor dem Norderheverkoog im Monatsmittel höhere energetische Kosten. Aus dem budgetierten Energieüberschuß (ΔE) wurde die theoretisch mögliche Reservestoffanlagerung (Änderung der Körpermasse) der Gänse berechnet. In Westerhever konnten die Gänse im Verlauf des Frühjahres 357 g Körperreserven anlagern. Bei den Gänsen vor dem Norderheverkoog waren es 399 g. Der Unterschied betrug 11,7 %, war aber nicht signifikant. Anhand von Fangdaten ist bekannt, daß Ringelgänse im langjährigen Mittel Körperreserven von 380 bis 400 Gramm anlagern. Die Störreizhäufigkeit des Tages bewirkte eine signifikante Veränderung der Budgetparameter DME und DEE und ΔE auf stündlicher Basis. In Westerhever stieg die Aufnahme an umsetzbarer Energie signifikant mit steigender Störreizhäufigkeit an. Vor dem Norderheverkoog verringerte sich diese jedoch signifikant. Die Energieaufwendungen stiegen in beiden Gebieten signifikant mit steigender Reizhäufigkeit an. Der Überschuß in der Energiebilanz der Gänse in Westerhever war an Tagen mit einer großen Störreizhäufigkeit um 8,7 % gegenüber den Tagen mit einer geringen Reizhäufigkeit verringert. Aufgrund fehlender kompensatorischer Nahrungsaufnahme war der Überschuß bei den Gänsen vor dem Norderheverkoog um maximal 27,5 % vermindert. Die Gänse in Westerhever haben störreizbedingte Zeitverluste bei der Nahrungsaufnahme und erhöhte energetische Kosten durch Verhaltensänderung und eine erhöhte Nahrungsaufnahme pro Zeit kompensiert. Aufgrund physiologischer Zwänge sind sie jedoch in dem stark vom Menschen beeinflußten Gebiet an die Grenzen ihrer Kompensationsmöglichkeit angelangt. Die errechnete Reservestoffanlagerung und auch der Jungvogelanteil im nachfolgenden Herbst waren geringer als bei den Gänsen vor dem Norderheverkoog.
    Notes: Abstract The impact of human disturbances on the energy budget of Brent Geese,Branta b. bernicla, during spring migration was investigated in two different salt marsh areas within the national park “Schleswig-Holsteinisches Wattenmeer”, Germany. We used the frequency of disturbance-related reactions of the birds as an indicator of the anthropogenic influencing of the sites. The disturbance frequency was significantly higher in the Westerhever salt marsh (1,5±0,7 reactions/h) than in the Norderheverkoog area (1,0±0,6 reactions/h). Monthly activity and energy budgets of the birds were calculated from March to May, based on several simultaneous day-round field observations per month. The amount of daily metabolizable energy (DME) was calculated via dropping rate and digestability of the food. The daily energy expenditure (DEE) was calculated by means of the time-energy-budget methods and by calculations, using the bodymass changes of caught birds during spring. With both methods very similar results were obtained; they varied between 0,4 to 4,5 % per areas and month. The daily energy budget (Æ E) was calculated from DEE — DME. Due to an increasing daily activity time from March to Mai the DME increased in both areas. Compared to the Norderheverkoog area the DME of the birds in Westerhever was higher in March and April, and similar in Mai. DEE increased in both areas too and was in all months higher in Westerhever than in Norderheverkoog. The calculated bodymass changes of the birds during spring was 357 g for the birds in Westerhever and 399 g for the birds in Norderheverkoog. Bodymass measures from caught birds revealed a mean mass gain of 380 to 400 g during spring. The daily disturbance frequency caused a significant change in the budget parameters DME, DDE and Δ E on a hourly base. In Westerhever DME/h increased, while in Norderheverkoog DME/h decreased significantly with increasing disturbance frequency. At the same time DEE/h increased in both areas significantly. As a consequence Δ E/h was reduced at days with a high disturbance frequency; in Westerhever by 8,7 % and in Norderheverkoog by 27,5%. In the disturbed area the birds compensated the time-loss during feeding and the higher energetic costs during disturbance-related flights by a change in activity pattern and by an increased food consumption per time unit. Based on physiological constraints the birds reached their compensatory abilities. The calculated bodymass gain and the proportion of young birds in the flocks was reduced in autumn.
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  • 17
    ISSN: 1434-601X
    Keywords: 25.75.+r
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Positively charged pions and protons from collisions of Ne+NaF and Au+Au at 1 GeV/nucleon incident energy were measured near midrapidity. The center-of-mass pion spectra deviate from a Maxwell-Boltzmann distribution. The slope of the high-energy part of the pion spectra varies significantly with the system mass and little with the size of the reaction zone. While the total pion yield rises linearly with the number of participant nucleons, the highenergy component increases more than linearly.
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  • 18
    Electronic Resource
    Electronic Resource
    Springer
    Cellular and molecular life sciences 52 (1996), S. 757-761 
    ISSN: 1420-9071
    Keywords: Vasculogenesis ; angiogenesis ; muscle ; embryonic ; metabolites ; fibroblast growth factor (FGF) ; chorioallantoic membrane (CAM)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract Normal and pathological formation of blood vessels is of considerable interest both in terms of basic scientific processes and clinical applications. Angiogenic events in the adult are likely to represent persistence of developmental mechanisms, and embryos are therefore a suitable experimental model for these processes. Among embryonic tissues, muscle is particularly appropriate for investigation, since it is highly vascularised from early stages. There are a number of competing explanations of how this process is controlled. Bioassays offer advantages over conventional molecular localisation techniques, in that they reveal the presence of active processed forms of the molecules under study, rather than non-processed forms, or non-translated meassages. Using these techniques, we report here that embryonic chick muscle, taken from the stages at which blood vessels are forming, produces an angiogenic activity on the chick chorioallantoic membrane (CAM), and transforms NR6 cells in soft agar. Basic fibroblast growth factor (bFGF) is shown to be angiogenic on the CAM in the same way, and also transforms NR6 cells (NR6 cells lack functional epidermal growth factor/transforming growth factor-a receptors, and are believed to respond only to bFGF in this way). Anti-bFGF removes the transforming activity of the embryonic muscle. We conclude that this represents evidence that embryonic chick muscle is producing an FGF-like molecule which is capable of acting as an angiogenic agent at the appropriate times in development.
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  • 19
    Electronic Resource
    Electronic Resource
    Springer
    Naturwissenschaften 9 (1921), S. 342-343 
    ISSN: 1432-1904
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Natural Sciences in General
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  • 20
    Electronic Resource
    Electronic Resource
    Springer
    Naturwissenschaften 8 (1920), S. 304-307 
    ISSN: 1432-1904
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Natural Sciences in General
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