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
Multidimensional transition state theory and the validity of Grote-Hynes theory
TL;DR: In this article, the Grote-Hynes theory of nonequilibrium solvation effects on reaction kinetics is examined using the perspective provided by multidimensional transition state theory for a model in which a solute reaction coordinate is bilinearally coupled to a harmonic solvent bath, and intermediate quantities that shed light on the ability of Grotehynes theory to capture relevant physical features of the reaction dynamics.
Book ChapterDOI
A Review of Enhanced Sampling Approaches for Accelerated Molecular Dynamics
TL;DR: A large range of statistical mechanics based enhanced sampling approaches have been proposed for accelerating molecular dynamics, and accessing timescales that are well beyond the reach of the fastest computers, and an overview of these approaches is provided.
Journal ArticleDOI
Dynamic effects on reaction rates in a Michael Addition catalyzed by Chalcone Isomerase. Beyond the frozen environment approach
TL;DR: Grote-Hynes (GH) theory provides a useful framework to systematically analyze all the couplings between the reaction coordinate and the remaining degrees of freedom, and provides transmission coefficients in excellent agreement with the Molecular Dynamics estimations.
Journal ArticleDOI
Coupling between protein and reaction dynamics in enzymatic processes: application of Grote-Hynes Theory to catechol O-methyltransferase.
TL;DR: Analysis of the transition state friction kernel leads to the identification of some key vibrational modes governing the coupling between the two different environments and the reacting solute in the Transition State Theory (TST) region and insights on their relevance for the reaction dynamics' influence on the transmission coefficient.
Journal ArticleDOI
Viscosity Dependence of the Local Segmental Dynamics of Anthracene-Labeled 1,2-Polybutadiene in Dilute Solution
TL;DR: In this article, the local segmental dynamics were observed in seven solvents covering a viscosity range of more than three decades and over the temperature range of 280−350 K.
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.