✦ LIBER ✦

Internal Reorganization Energy Contributed by Torsional Motion in Electron Transfer Reaction between Biphenyl and Biphenyl Anion Radical

✍ Scribed by Wei Min; Lin Sun

Publisher: John Wiley and Sons
Year: 2010
Tongue: English
Weight: 374 KB
Volume: 20
Category: Article
ISSN: 0256-7660
DOI: 10.1002/cjoc.20020201008

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✦ Synopsis

Abstract

Concerning the theoretical estimation of internal reorganization energy contributed by the tortional motion between biphenyl and biphenyl anion radical, direct calculation of self‐exchange electron transfer reaction was investigated. With the introduction of a proper average bond length and angle parameters (bond Bp), a multiple step relaxation Nelson method was developed to deal with the torsional reorganization energy. Based on the above model, an estimation of pure torsional reorganization energy λ~t.p~ with an approximation of λ~t.1~ was achieved. The results of 0.140 and 0.125 eV of torsional reorganization energy for a cross‐reaction at the levels of 4‐31G and HP/DZP, respectively, are in good agreement with the value of 0.13 eV obtained by Miller et al. from the rate measurements. This implies the efficiency and validity of our method to estimate the reorganization energy contributed by pure torsional motion of Bp.

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