Title: Extension of Hopfield’s Electron Transfer Model To Accommodate Site–Site Correlation

Abstract

Extension of the Förster analogue for the ET rate constant (based on virtual intermediate electron detachment or attachment states) with inclusion of site–site correlation due to coulomb terms associated with solvent reorganization energy and the driving force, has been developed and illustrated for a simple three-state, two-mode model. Furthermore, the model is applicable to charge separation (CS), recombination (CR), and shift (CSh) ET processes, with or without an intervening bridge. The model provides a unified perspective on the role of virtual intermediate states in accounting for the thermal Franck–Condon weighted density of states (FCWD), the gaps controlling superexchange coupling, and mean absolute redox potentials, with full accommodation of site–site coulomb interactions. We analyzed two types of correlation: aside from the site–site correlation due to coulomb interactions, we have emphasized the intrinsic “nonorthogonality” which generally pertains to reaction coordinates (RCs) for different ET processes involving multiple electronic states, as may be expressed by suitably defined direction cosines (cos(θ)). A pair of RCs may be nonorthogonal even when the site–site coulomb correlations are absent. While different RCs are linearly independent in the mathematical sense for all θ ≠ 0°, they are independent in the sense of being “uncorrelated” only in the limitmore » of orthogonality (θ = 90°). There is application to more than two coordinates is straightforward and may include both discrete and continuum contributions.« less

Authors:

Newton, Marshall D. ^[1]

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+ Show Author Affiliations

1. Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Chemistry

Publication Date:

Mon Oct 26 00:00:00 EDT 2015

Research Org.:

Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:

1335383

Report Number(s):

BNL-111780-2016-JA
Journal ID: ISSN 1520-6106; R&D Project: CO004; KC0304030

Grant/Contract Number:  

SC00112704

Resource Type:

Accepted Manuscript

Journal Name:

Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

Additional Journal Information:

Journal Volume: 119; Journal Issue: 46; Journal ID: ISSN 1520-6106

Publisher:

American Chemical Society

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY