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Journal ArticleDOI

The stable states picture of chemical reactions. II. Rate constants for condensed and gas phase reaction models

Richard F. Grote, +1 more
- 15 Sep 1980 - 
- Vol. 73, Iss: 6, pp 2715-2732
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.

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Citations
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Journal ArticleDOI

Effects of solvent on TMP photophysics. Transition from no barrier to barrier case, induced by solvent properties

TL;DR: In this paper, the authors studied the radiationless relaxation of triphenylmethane (TPM) molecules in the n-alcohols methanol to octadecanol with picosecond absorption recovery techniques as a function of viscosity, temperature and wavelength of the exciting and analyzing light.
Journal ArticleDOI

Fluorescence upconversion study of cis‐stilbene isomerization

TL;DR: In this paper, the isomerization dynamics of cis-stilbene in the first excited singlet state were studied by the technique of fluorescence upconversion, and lifetime measurements were made with subpicosecond resolution in 2-propanol, decanol, n−hexane, and tetradecane.
Journal ArticleDOI

Quantum dynamics in low-temperature chemistry

TL;DR: A contemporary review of quantum models of chemical reactions is presented in this paper, where the correlation between the quantum rate constant and spectral properties of the heat bath and dynamics of intramolecular vibrations is considered.
Journal ArticleDOI

Ab Initio Evaluation of the Potential Surface for General Base- Catalyzed Methanolysis of Formamide: A Reference Solution Reaction for Studies of Serine Proteases

TL;DR: In this article, the reference solution reaction for studies of serine proteases, i.e., the base-catalyzed and general base/acid catalyzed methanolysis of formamide, was investigated.
Journal ArticleDOI

Dynamics of the isomerization of trans-stilbene in n-alcohols studied by ultraviolet picosecond absorption recovery

TL;DR: In this paper, a simple At + synchronously pumped and cavity-dumped dye-laser system was used to generate UV picosecond pulses with energies sufficiently high for absorption recovery experiments.
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.
Book

Theory of Unimolecular Reactions

W. Forst, +1 more
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.
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