Variational transition state theory for electron transfer reactions in solution

Benjamin, Ilan; Pollak, Eli

doi:10.1063/1.472743

Cited by 11 publications

(4 citation statements)

References 70 publications

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“…13, it was demonstrated that the proton transfer in a strongly H‐bonded complex takes place in 20–30 fs whereas the solvent response is delayed by about 50 fs. In such cases, molecular dynamics (MD) simulation or theory based on the Langevin equation analysis15–20 would give us a more realistic description of the solvation effect than the former methods. In the classical MD simulation, however, one has to optimize charge parameters for the reacting solutes separately for all the configurations of interest along the reaction coordinate.…”

Section: Introductionmentioning

confidence: 99%

Hybrid QM/MM molecular dynamics simulations for an ionic S_N2 reaction in the supercritical water: OH⁻ + CH₃Cl → CH₃OH + Cl⁻

2002

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A hybrid real space quantum mechanical/molecular mechanical (RS-QM/MM) method has been applied to an ionic S(N)2 reaction (OH- + CH3Cl --> CH3OH + Cl-) in water solution to investigate dynamic solvation effects of the supercritical water (SCW) on the reaction. It has been demonstrated that the approaching process of OH- to methyl group is prevented by water molecules in the ambient water (AW), while the reaction takes place easily in the gas phase. Almost the same solvation effect on the dynamics of OH- is observed in the SCW, though the bulk density of water is substantially reduced compared with that of the AW. It has been shown that the solvation of the SCW around the OH anion is locally identical to that of the AW due to the strong ion-dipole interactions between OH- and water molecules. At the transition state, the QM/MM simulations have revealed that the excess electron is quite flexible, and the charge volume, as well as the fractional charges on atoms, vary seriously depending on the instantaneous solvent configurations. However, it has been found that the solvation energy in the SCW can be qualitatively related to the HOMO volume of the system by Born's equation.

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Section: Introductionmentioning

confidence: 99%

Hybrid QM/MM molecular dynamics simulations for an ionic S_N2 reaction in the supercritical water: OH⁻ + CH₃Cl → CH₃OH + Cl⁻

2002

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“…A turnover should also be observed when considering the effect of friction on non‐adiabatic transitions. Some progress has been made in the spatial diffusion‐limited regime [92–95] . However, the turnover theory as formulated at present is limited to adiabatic, single‐surface dynamics.…”

Section: Discussionmentioning

confidence: 99%

“…Some progress has been made in the spatial diffusion-limited regime. [92][93][94][95] However, the turnover theory as formulated at present is limited to adiabatic, single-surface dynamics. Both theoretical extensions of the turnover theory, as well as numerically exact quantum simulations, would be needed to verify the effect.…”

Section: Discussionmentioning

confidence: 99%

Recent Developments in Kramers’ Theory of Reaction Rates

Pollak

Miret‐Artés

2023

ChemPhysChem

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In this short review, we provide an update of recent developments in Kramers’ theory of reaction rates. After a brief introduction stressing the importance of this theory initially developed for chemical reactions, we briefly present the main theoretical formalism starting from the generalized Langevin equation and continue by showing the main points of the modern Pollak, Grabert and Hänggi theory. Kramers’ theory is then sketched for quantum and classical surface diffusion. As an illustration the surface diffusion of Na atoms on a Cu(110) surface is discussed showing escape rates, jump distributions and diffusion coefficients as a function of reduced friction. Finally, some very recent applications of turnover theory to different fields such as nanoparticle levitation, microcavity polariton dynamics and simulation of reaction in liquids are presented. We end with several open problems and future challenges faced up by Kramers turnover theory.

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“…The one close to the present approach is the variational transition state theory proposed by Rips and Pollak and others. 24,[40][41][42] They introduced the collective system-bath coordinate, which is characterized by a maximal mean-free path in the vicinity of crossing point. They have also demonstrated that the energy gap coordinate of the two electronic states provides a good description of the ET dynamics in the fast relaxation limit, which is consistent with the present approach, but cannot be appropriate in the strong solvent friction, and that the optimization approach has to be employed to find an effective coordinate.…”

Section: Discussionmentioning

confidence: 99%

Semiclassical Treatment of Thermally Activated Electron Transfer in the Inverted Region under the Fast Dielectric Relaxation

et al. 2007

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The previously formulated semiclassical theory (Zhao, Liang, and Nakamura, J. Phys. Chem. A 2006, 110, 8204) is used to study electron transfer in the Marcus inverted case by considering multidimensional potential energy surfaces of donor and acceptor. The Zhu-Nakamura formulas of nonadiabatic transition in the case of Landau-Zener type are incorporated into the approach. The theory properly takes into account the nonadiabatic transition coupled with the nuclear tunneling and can cover the whole range from weak to strong coupling regime uniformly under the assumption of fast solvent relaxation. The numerical calculations are performed for the 12-dimensional model of shifted harmonic oscillators and demonstrate that the reaction rate with respect to the electronic coupling shows a maximum, confirming the adiabatic suppression in the strong coupling limit. The adiabatic suppression is dramatically reduced by the effect of nuclear tunneling compared to the case that the Landau-Zener formula is used. The possible extension and applications to the case of the slow solvent dynamics are discussed.

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Variational transition state theory for electron transfer reactions in solution

Abstract: Classical trajectory and adiabatic channel study of the transition from adiabatic to sudden capture dynamics. III. Dipole-dipole capture

Cited by 11 publications

References 70 publications

Hybrid QM/MM molecular dynamics simulations for an ionic S_N2 reaction in the supercritical water: OH⁻ + CH₃Cl → CH₃OH + Cl⁻

Hybrid QM/MM molecular dynamics simulations for an ionic S_N2 reaction in the supercritical water: OH⁻ + CH₃Cl → CH₃OH + Cl⁻

Recent Developments in Kramers’ Theory of Reaction Rates

Semiclassical Treatment of Thermally Activated Electron Transfer in the Inverted Region under the Fast Dielectric Relaxation

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Variational transition state theory for electron transfer reactions in solution

Abstract: Classical trajectory and adiabatic channel study of the transition from adiabatic to sudden capture dynamics. III. Dipole-dipole capture

Cited by 11 publications

References 70 publications

Hybrid QM/MM molecular dynamics simulations for an ionic SN2 reaction in the supercritical water: OH− + CH3Cl → CH3OH + Cl−

Hybrid QM/MM molecular dynamics simulations for an ionic SN2 reaction in the supercritical water: OH− + CH3Cl → CH3OH + Cl−

Recent Developments in Kramers’ Theory of Reaction Rates

Semiclassical Treatment of Thermally Activated Electron Transfer in the Inverted Region under the Fast Dielectric Relaxation

Contact Info

Product

Resources

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Hybrid QM/MM molecular dynamics simulations for an ionic S_N2 reaction in the supercritical water: OH⁻ + CH₃Cl → CH₃OH + Cl⁻

Hybrid QM/MM molecular dynamics simulations for an ionic S_N2 reaction in the supercritical water: OH⁻ + CH₃Cl → CH₃OH + Cl⁻