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
More filters
Journal ArticleDOI
Memory effects on stochastic resonance
Alexander Neiman,Wokyung Sung +1 more
TL;DR: In this article, the authors studied the phenomenon of stochastic resonance in a bistable system with internal colored noise, and they showed that memory usually suppresses this phenomenon, however, for a large memory time SR can be enhanced by the memory.
Journal ArticleDOI
The rate of electrochemical electron-transfer reactions
W. Schmickler,J. Mohr +1 more
TL;DR: In this paper, the rate of electron exchange is calculated by a combination of quantum mechanics and computer simulations for all strengths of the electronic interaction, so that the dependence of the reaction rate on the interaction strength could be obtained.
Journal ArticleDOI
Perspective: Bimolecular chemical reaction dynamics in liquids
TL;DR: Progress is examined in the use of time-resolved infra-red spectroscopy to study reaction dynamics in liquids, how existing theories can guide the interpretation of experimental data is discussed, and future challenges for this field of research are suggested.
Journal ArticleDOI
Solvent-Controlled Intramolecular Electron Transfer in Ionic Liquids
TL;DR: The present results demonstrate that the same equality between (integral) reaction times and solvation times observed in conventional solvents also applies in ionic liquids.
Journal ArticleDOI
Reorganization energies and rate constants for electron reactions in glass-forming media and proteins
Brian M. Hoffman,Mark A. Ratner +1 more
TL;DR: In this paper, a temperature dependent reorganization energy was introduced to model the non-equilibrium effects of intramolecular electron transfer in glassy solvents and proteins which themselves undergo glassing transitions.
References
More filters
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.