A two-dimensional Born-Oppenheimer treatment of intramolecular electron transfer reactions

M. V. Basilevsky; I. V. Rostov; M. D. Newton

doi:10.1016/S0022-0728(97)00619-0

A two-dimensional Born-Oppenheimer treatment of intramolecular electron transfer reactions

M. V. Basilevsky^*, I. V. Rostov, M. D. Newton

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

9 Citations (Scopus)

Abstract

The Born-Oppenheimer (BO) formulation of polar solvation is developed and implemented at the semiemperical (PM3) configuration interaction (CI) level, yielding estimates of electron transfer (ET) coupling elements (V₀) for intramolecular ET in several families of radical ion systems. In contrast to the traditional treatment based on a single solvent coordinate and a fixed gas-phase coupling element, the present treatment yields a self-consistent characterization of kinetic parameters in a 2-dimensional solvent framework which includes an exchange coordinate. The dependence of V₀ on inertial solvent contributions and on donor/acceptor separation (r_DA) is discussed.

Original language	English
Pages (from-to)	69-82
Number of pages	14
Journal	Journal of Electroanalytical Chemistry
Volume	450
Issue number	1
DOIs	https://doi.org/10.1016/S0022-0728(97)00619-0
Publication status	Published - 15 Jun 1998
Externally published	Yes

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10.1016/S0022-0728(97)00619-0

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title = "A two-dimensional Born-Oppenheimer treatment of intramolecular electron transfer reactions",

abstract = "The Born-Oppenheimer (BO) formulation of polar solvation is developed and implemented at the semiemperical (PM3) configuration interaction (CI) level, yielding estimates of electron transfer (ET) coupling elements (V0) for intramolecular ET in several families of radical ion systems. In contrast to the traditional treatment based on a single solvent coordinate and a fixed gas-phase coupling element, the present treatment yields a self-consistent characterization of kinetic parameters in a 2-dimensional solvent framework which includes an exchange coordinate. The dependence of V0 on inertial solvent contributions and on donor/acceptor separation (rDA) is discussed.",

author = "Basilevsky, {M. V.} and Rostov, {I. V.} and Newton, {M. D.}",

year = "1998",

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T1 - A two-dimensional Born-Oppenheimer treatment of intramolecular electron transfer reactions

AU - Basilevsky, M. V.

AU - Rostov, I. V.

AU - Newton, M. D.

PY - 1998/6/15

Y1 - 1998/6/15

N2 - The Born-Oppenheimer (BO) formulation of polar solvation is developed and implemented at the semiemperical (PM3) configuration interaction (CI) level, yielding estimates of electron transfer (ET) coupling elements (V0) for intramolecular ET in several families of radical ion systems. In contrast to the traditional treatment based on a single solvent coordinate and a fixed gas-phase coupling element, the present treatment yields a self-consistent characterization of kinetic parameters in a 2-dimensional solvent framework which includes an exchange coordinate. The dependence of V0 on inertial solvent contributions and on donor/acceptor separation (rDA) is discussed.

AB - The Born-Oppenheimer (BO) formulation of polar solvation is developed and implemented at the semiemperical (PM3) configuration interaction (CI) level, yielding estimates of electron transfer (ET) coupling elements (V0) for intramolecular ET in several families of radical ion systems. In contrast to the traditional treatment based on a single solvent coordinate and a fixed gas-phase coupling element, the present treatment yields a self-consistent characterization of kinetic parameters in a 2-dimensional solvent framework which includes an exchange coordinate. The dependence of V0 on inertial solvent contributions and on donor/acceptor separation (rDA) is discussed.

UR - http://www.scopus.com/inward/record.url?scp=0032089470&partnerID=8YFLogxK

U2 - 10.1016/S0022-0728(97)00619-0

DO - 10.1016/S0022-0728(97)00619-0

M3 - Article

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VL - 450

SP - 69

EP - 82

JO - Journal of Electroanalytical Chemistry

JF - Journal of Electroanalytical Chemistry

IS - 1

ER -

A two-dimensional Born-Oppenheimer treatment of intramolecular electron transfer reactions

Abstract

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