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
Solution of phase space diffusion equations using interacting trajectory ensembles
Arnaldo Donoso,Craig C. Martens +1 more
TL;DR: In this paper, a deterministic trajectory-based approach to the solution of condensed phase dynamics and chemical reactions is presented, based on the propagation of ensembles of trajectories.
Journal ArticleDOI
Ultrafast equilibrium and non-equilibrium chemical reaction dynamics probed with multidimensional infrared spectroscopy
TL;DR: Two-dimensional infrared (2D-IR) spectroscopy provides powerful tools to investigate chemical reaction dynamics in the condensed phase as discussed by the authors, and it can monitor the picosecond dynamics of non-triggered chemical reactions by correlating excited reactant frequencies with detected product frequencies.
Journal ArticleDOI
Solvent and frequency dependence of vibrational dephasing on femtosecond time-scales
Peter Vöhringer,R. A. Westervelt,T.-S. Yang,David C. Arnett,Mark J. Feldstein,Norbert F. Scherer +5 more
TL;DR: In this article, the results of degenerate wavenumber third-order polarization (pump-probe) measurements of vibrational dephasing and relaxation in a variety of solvents are reported.
Journal ArticleDOI
On the Dissociation of Aromatic Radical Anions in Solution. 2. Reaction Path and Rate Constant Analysis
TL;DR: In this article, a transition state theory (TSTTST) rate constant for the radical anion dissociation in solution has been proposed and compared with a conventional equilibrium solvation perspective, and dissipative frictional effects on the reaction rate are examined and determined to be negligible.
Journal ArticleDOI
Centroid‐density quantum rate theory: Variational optimization of the dividing surface
TL;DR: McRae et al. as discussed by the authors presented a generalization of Feynman path integral quantum activated rate theory that has classical variational transition state theory as its foundation and recast the expression for the rate constant in a form that mimics the phase-space integration over a dividing surface that is found in the classical theory.
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.