Theory of the self-exchange electron transfer in the dioxygen/superoxide system in water

Ernst D. German; Alexander M. Kuznetsov; Irina Efremenko; Moshe Sheintuch

doi:10.1021/jp9920141

Theory of the self-exchange electron transfer in the dioxygen/superoxide system in water

Ernst D. German^*, Alexander M. Kuznetsov, Irina Efremenko, Moshe Sheintuch

^*Corresponding author for this work

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

11 Scopus citations

Abstract

Theoretical investigation of the rate constant and activation energy of the charge-transfer reaction in water is performed. Equations for these kinetic characteristics of the reaction obtained in the framework of quantum mechanical theory are presented. The equations take into account a quantum character of the O-O vibration and the fact that the dielectric spectrum.of^water has an absorption in the quantum frequency range. Parameters of these equations, such as the reactants' interaction free energy in water, U(R), electron coupling matrix element, V_fi, and reorganization energies are calculated in terms of appropriate models for several mutual geometries of the reactants. For each of these geometries, the distance dependence of the parameters is investigated and used for numerical estimation of the rate constant and activation energy. Results of the theoretical analysis are in a reasonable agreement with experimental data.

Original language	English
Pages (from-to)	10699-10707
Number of pages	9
Journal	Journal of Physical Chemistry A
Volume	103
Issue number	50
DOIs	https://doi.org/10.1021/jp9920141
State	Published - 16 Dec 1999
Externally published	Yes

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title = "Theory of the self-exchange electron transfer in the dioxygen/superoxide system in water",

abstract = "Theoretical investigation of the rate constant and activation energy of the charge-transfer reaction in water is performed. Equations for these kinetic characteristics of the reaction obtained in the framework of quantum mechanical theory are presented. The equations take into account a quantum character of the O-O vibration and the fact that the dielectric spectrum.of^water has an absorption in the quantum frequency range. Parameters of these equations, such as the reactants' interaction free energy in water, U(R), electron coupling matrix element, Vfi, and reorganization energies are calculated in terms of appropriate models for several mutual geometries of the reactants. For each of these geometries, the distance dependence of the parameters is investigated and used for numerical estimation of the rate constant and activation energy. Results of the theoretical analysis are in a reasonable agreement with experimental data.",

author = "German, {Ernst D.} and Kuznetsov, {Alexander M.} and Irina Efremenko and Moshe Sheintuch",

year = "1999",

month = dec,

day = "16",

doi = "10.1021/jp9920141",

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volume = "103",

pages = "10699--10707",

journal = "Journal of Physical Chemistry A",

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TY - JOUR

T1 - Theory of the self-exchange electron transfer in the dioxygen/superoxide system in water

AU - German, Ernst D.

AU - Kuznetsov, Alexander M.

AU - Efremenko, Irina

AU - Sheintuch, Moshe

PY - 1999/12/16

Y1 - 1999/12/16

N2 - Theoretical investigation of the rate constant and activation energy of the charge-transfer reaction in water is performed. Equations for these kinetic characteristics of the reaction obtained in the framework of quantum mechanical theory are presented. The equations take into account a quantum character of the O-O vibration and the fact that the dielectric spectrum.of^water has an absorption in the quantum frequency range. Parameters of these equations, such as the reactants' interaction free energy in water, U(R), electron coupling matrix element, Vfi, and reorganization energies are calculated in terms of appropriate models for several mutual geometries of the reactants. For each of these geometries, the distance dependence of the parameters is investigated and used for numerical estimation of the rate constant and activation energy. Results of the theoretical analysis are in a reasonable agreement with experimental data.

AB - Theoretical investigation of the rate constant and activation energy of the charge-transfer reaction in water is performed. Equations for these kinetic characteristics of the reaction obtained in the framework of quantum mechanical theory are presented. The equations take into account a quantum character of the O-O vibration and the fact that the dielectric spectrum.of^water has an absorption in the quantum frequency range. Parameters of these equations, such as the reactants' interaction free energy in water, U(R), electron coupling matrix element, Vfi, and reorganization energies are calculated in terms of appropriate models for several mutual geometries of the reactants. For each of these geometries, the distance dependence of the parameters is investigated and used for numerical estimation of the rate constant and activation energy. Results of the theoretical analysis are in a reasonable agreement with experimental data.

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U2 - 10.1021/jp9920141

DO - 10.1021/jp9920141

M3 - 文章

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SN - 1089-5639

VL - 103

SP - 10699

EP - 10707

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 50

ER -

Theory of the self-exchange electron transfer in the dioxygen/superoxide system in water

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