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Scientific article
English

Temperature Effect on Back Electron-Transfer Reactions within a Geminate Radical Pair: the Influence of the Solvent on the Adiabaticity of the Process

Contributors

Vauthey, Eric; Suppan, Paul

Published in

Chemical physics, vol. 139, no. 2-3, p. 381-390

Publication date

1989

Abstract

A study of the temperature dependence (from 233 to 353 K) of the rate of back electron-transfer reactions within geminate radical pairs by measurement of the free radical yield is reported. The radical pair is generated by photoinduced electron transfer with rhodamine 6G and oxazine 118 cations as electron acceptors and aromatic amines and methoxy-benzene derivatives as electron donors in acetonitrile, methanol and ethanol. In acetonitrile, the back electron transfer is non-adiabatic and apparent negative activation energies are observed for barrierless reactions. In alcohol solvents, an anomalously large temperature dependence is observed, which is attributed to a solvent-controlled adiabatic behaviour.

UNIGE affiliation entities

UNIGE research groups

Citation (ISO format)

VAUTHEY, Eric, SUPPAN, Paul. Temperature Effect on Back Electron-Transfer Reactions within a Geminate Radical Pair: the Influence of the Solvent on the Adiabaticity of the Process. In: Chemical physics, 1989, vol. 139, n° 2-3, p. 381–390. doi: 10.1016/0301-0104(89)80150-8

Identifiers

Journal ISSN

0301-0104
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Technical informations

Creation

21/09/2009 16:19:59

First validation

21/09/2009 16:19:59

Update

14/03/2023 15:13:22

Status update

14/03/2023 15:13:22

Last indexation

29/10/2024 12:08:56
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