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The Journal of Chemical Physics
Article . 2005 . Peer-reviewed
Data sources: Crossref
https://dx.doi.org/10.48550/ar...
Article . 2005
License: arXiv Non-Exclusive Distribution
Data sources: Datacite
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Stochastic transition states: Reaction geometry amidst noise

Authors: Bartsch, Thomas; Uzer, Turgay; Hernandez, Rigoberto;

Stochastic transition states: Reaction geometry amidst noise

Abstract

Classical transition state theory (TST) is the cornerstone of reaction-rate theory. It postulates a partition of phase space into reactant and product regions, which are separated by a dividing surface that reactive trajectories must cross. In order not to overestimate the reaction rate, the dynamics must be free of recrossings of the dividing surface. This no-recrossing rule is difficult (and sometimes impossible) to enforce, however, when a chemical reaction takes place in a fluctuating environment such as a liquid. High-accuracy approximations to the rate are well known when the solvent forces are treated using stochastic representations, though again, exact no-recrossing surfaces have not been available. To generalize the exact limit of TST to reactive systems driven by noise, we introduce a time-dependent dividing surface that is stochastically moving in phase space, such that it is crossed once and only once by each transition path.

Country
United States
Related Organizations
Keywords

Statistical Mechanics (cond-mat.stat-mech), Chemical reactions, Reaction kinetics theory, FOS: Physical sciences, Noise, 541, Condensed Matter - Statistical Mechanics

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    influence
    This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
54
Top 10%
Top 10%
Average
Green
bronze