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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Book ChapterDOI
Collective Orientational Relaxation in Dense Dipolar Liquids
Biman Bagchi,Amalendu Chandra +1 more
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Theory of activated rate processes for arbitrary frequency dependent friction: Solution of the turnover problem
TL;DR: In this article, an analytical theory for the thermal (classical mechanical) rate of escape from a metastable state coupled to a dissipative thermal environment is formulated, and the working expressions are given solely in terms of the quantities entering the generalized Langevin equation for the particle dynamics.
Journal ArticleDOI
Ultrafast Elementary Photochemical Processes of Organic Molecules in Liquid Solution
TL;DR: Reactions discussed include intra- and intermolecular electron- and proton-transfer processes, as well as photochromic reactions occurring with and without bond breaking or bond formation, namely ring-opening reactions and cis-trans isomerizations, respectively.
Journal ArticleDOI
Molecular dynamics of a model SN1 reaction in water
TL;DR: In this article, a computer simulation of the dynamics of a model SN1 reaction in water, very loosely based on the reaction t•BuCl→t•Bu++Cl−, is presented.
Journal ArticleDOI
Ultrafast solvation dynamics explored by femtosecond photon echo spectroscopies
TL;DR: In this article, various forms of photon echo (time-integrated, time-gated, and heterodyne-detected photon echo) as well as Fourier transform spectral interferometry are discussed.
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.