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  • 1
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 109 (1998), S. 1125-1133 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: We apply a stochastic method introduced by Dellago et al. [J. Chem. Phys. 108, 1964 (1998)] to sample transition paths in high-dimensional systems. The method connects two endpoint regions (for example a reactant and a product region) by a set of space-time paths. This approach is an importance sampling for rare events that does not require prior knowledge of the location of dynamical bottlenecks. Transition paths are generated with a weight corresponding to a chain of Metropolis Monte Carlo steps. We derive Monte Carlo algorithms and apply the technique to the dynamics of hydrogen-bond breaking in liquid water. We obtain averages in a transition path ensemble for the structure and energy along the trajectory. While characterized by a rate constant, hydrogen-bond breaking in water occurs frequently enough to be studied by standard methods. The process therefore provides a useful test of path sampling methods. The comparison between path sampling and standard Monte Carlo demonstrate the feasibility of transition path sampling for a many-body system with a rough potential energy surface. © 1998 American Institute of Physics.
    Materialart: Digitale Medien
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  • 2
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 108 (1998), S. 1964-1977 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: We have developed a method to study transition pathways for rare events in complex systems. The method can be used to determine rate constants for transitions between stable states by turning the calculation of reactive flux correlation functions into the computation of an isomorphic reversible work. In contrast to previous dynamical approaches, the method relies neither on prior knowledge nor on explicit specification of transition states. Rather, it provides an importance sampling from which transition states can be characterized statistically. A simple model is analyzed to illustrate the methodology. © 1998 American Institute of Physics.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 108 (1998), S. 9050-9061 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: A generalized Falicov–Kimball model is applied to study the phase diagram of metal ammonia solutions. The model includes a fluid–fluid interaction term and an electron–fluid interaction with a hard core and an attractive tail. Mean-field theories are derived for the localized and delocalized electron phases using ideas from the slave-boson approach to the Hubbard model. The attractive force stabilizes both the homogeneous delocalized electron phase and a regime where the electrons localize in cavities devoid of fluid particles. In its absence, the localized states are found to be unstable towards phase separation, in contrast to previous predictions. The Gaussian fluctuations and structure factors derived from this theory suggest the existence of bicontinuous channels percolating through the system. These findings agree qualitatively with experiments and computer simulations. © 1998 American Institute of Physics.
    Materialart: Digitale Medien
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