Method of splitting polarization coordinates for description of ultrafast multistage electron transfer in a non-debye medium

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Abstract

A method for constructing the space of medium states in reactions of ultrafast multistage intramolecular electron transfer in media with several relaxation times is developed. The method uses the splitting of polarization coordinates into relaxation components, and is a generalization of two previously developed approaches used (1) to describe multistage reactions, and (2) to consider multicomponent relaxation. Within the suggested generalized scheme, a model of charge transfer in a three-center molecular system in the environment with a two-component relaxation function is considered, an algorithm for constructing the diabatic free energy surfaces of electronic states is described, a system of equations for the evolution of the distribution functions is written. The results of the general model are shown to reproduce well-known solutions in particular cases.

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S. V. Feskov

Volgograd State University

Author for correspondence.
Email: serguei.feskov@volsu.ru
Russian Federation, Volgograd

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2. Fig. 1. a - Free energy surfaces G of electronic states of a three-center system | φ 1 〉 = D*A1A2, | φ 2 〉 = D+A1–A2 and | φ 3 〉 = D+A1A2– in the space of polarization coordinates Q1 and Q2. obtained by orthogonal projection from the extended space q into the subspace Q, the values ​​of the model parameters are indicated in the text; b — location of the PSE minimum points on the plane (Q1, Q2). The displacement vectors Dnn′ and the angle q, which determines the correlation between electronic transitions, are indicated | φ 1 〉 → | φ 2 〉 and | φ 1 〉 → | φ 3〉.

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3. Fig. 2. a — Free energy surfaces G of the system in the subspace of relaxation coordinates R, obtained by orthogonal projection from the space q. The values ​​of the model parameters are the same as in Fig. 1. The values ​​of the weighting coefficients x1 and x2 correspond to acetonitrile (indicated in the text). b - Location of minimum PSE points on the plane (R1, R2) - along a straight line specified by the equation R2 / R1 = x2 / x1.

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