Journal ArticleDOI
The stable states picture of chemical reactions. II. Rate constants for condensed and gas phase reaction models
Richard F. Grote,James T. Hynes +1 more
TLDR
In this paper, the stable states picture (SSP) was used to derive the time correlation function (tcf) for the rate constant κ for a wide variety of gas and solution phase reaction models.Abstract:
The time correlation function (tcf) formulas for rate constants κ derived via the stable states picture (SSP) of chemical reactions are applied to a wide variety (a–d) of gas and solution phase reactionmodels. (a) For gas phase bimolecular reactions, we show that the flux tcf governing κ corresponds to standard numerical trajectory calculation methods. Alternate formulas for κ are derived which focus on saddle point surfaces, thus increasing computational efficiency. Advantages of the SSP formulas for κ are discussed. (b) For gas phase unimolecular reactions, simple results for κ are found in both the strong and weak coupling collision limits; the often ignored role of product stabilization is exposed for reversible isomerizations. The SSP results correct some standard weak coupling rate constant results by as much as 50%. (c) For barrier crossing reactions in solution, we evaluate κ for a generalized (non‐Markovian) Langevin description of the dynamics. For several realistic models of time dependent friction, κ differs dramatically from the popular Kramers constant friction predictions; this has important implications for the validity of transition state theory. (d) For solutionreactions heavily influenced by spatial diffusion, we show that the SSP isolates short range reaction dynamics of interest and includes important barrier region effects in structural isomerizations often missed in standard descriptions.read more
Citations
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Journal ArticleDOI
Critical comparison of approximate and accurate quantum-mechanical calculations of rate constants for a model activated reaction in solution
Robin P. McRae,Gregory K. Schenter,Bruce C. Garrett,George R. Haynes,Gregory A. Voth,George C. Schatz +5 more
TL;DR: In this article, the authors compared the performance of two approximate methods: variational transition state theory with semiclassical corrections for reaction coordinate motion, and the pathintegral centroid density method.
Journal ArticleDOI
The Pre-exponential Factor in Electrochemistry.
TL;DR: This Minireview will show that the time has come for a third cycle based on recent progress in electrocatalysis, and discusses a general concept of kinetics-the pre-exponential factor of a rate constant-which has undergone two such cycles.
Journal ArticleDOI
Molecular Mechanism of Specific Ion Interactions between Alkali Cations and Acetate Anion in Aqueous Solution: A Molecular Dynamics Study
TL;DR: Upon analyzing the computed free energy profiles for the Na(+)/K(+)-acetate ion-pairs, it is observed a deeper contact ion minimum and also a larger association constant for theNa(+-acetate pair as compared to the corresponding K(+); these observations help to demonstrate the preferential binding of Na(+) over K(+) to protein surfaces.
Journal ArticleDOI
Interplay of non-Markov and internal friction effects in the barrier crossing kinetics of biopolymers: insights from an analytically solvable model.
TL;DR: These effects are illustrated using an analytically solvable toy model of an unstructured polymer chain involved in an inter- or intramolecular transition and the transition rate is calculated using the Grote-Hynes and Langer theories, which account for memory.
Journal ArticleDOI
The non-Markovian quantum master equation in the collective-mode representation: application to barrier crossing in the intermediate friction regime.
Anna Pomyalov,David J. Tannor +1 more
TL;DR: This paper shows that by augmenting the system coordinate with a collective mode of the bath, the regime of validity of the non-Markovian master equation can be extended significantly, up to dimensionless frictions of 0.5 over the entire temperature range.
References
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Journal ArticleDOI
Brownian motion in a field of force and the diffusion model of chemical reactions
TL;DR: In this article, a particle which is caught in a potential hole and which, through the shuttling action of Brownian motion, can escape over a potential barrier yields a suitable model for elucidating the applicability of the transition state method for calculating the rate of chemical reactions.
BookDOI
Dynamics of Molecular Collisions
TL;DR: In this paper, the potential energy surfaces and their effect on collision processes are discussed. But the authors focus on the nonadiabatic processes in collision theory and not on the classical trajectories of trajectories.