Transient Exciplex Formation Electron Transfer Mechanism | Zendy

M. G. Kuz’min | Zendy; И. В. Соболева | Zendy; E. V. Dolotova | Zendy

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Transient Exciplex Formation Electron Transfer Mechanism

Author(s) -

M. G. Kuz’min,

И. В. Соболева,

E. V. Dolotova

Publication year - 2011

Publication title -

advances in physical chemistry

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 0.269

H-Index - 17

eISSN - 1687-7993

pISSN - 1687-7985

DOI - 10.1155/2011/813987

Subject(s) - excimer , chemistry , electron transfer , excited state , chemical physics , kinetics , reaction mechanism , photochemistry , electron , enthalpy , mechanism (biology) , thermodynamics , atomic physics , fluorescence , catalysis , physics , biochemistry , quantum mechanics

Transient exciplex formation mechanism of excited-state electron transfer reactions is analyzed in terms of experimental data on thermodynamics and kinetics of exciplex formation and decay. Experimental profiles of free energy, enthalpy, and entropy for transient exciplex formation and decay are considered for several electron transfer reactions in various solvents. Strong electronic coupling in contact pairs of reactants causes substantial decrease of activation energy relative to that for conventional long-range ET mechanism, especially for endergonic reactions, and provides the possibility for medium reorganization concatenated to gradual charge shift in contrast to conventional preliminary medium and reactants reorganization. Experimental criteria for transient exciplex formation (concatenated) mechanism of excited-state electron transfer are considered. Available experimental data show that this mechanism dominates for endergonic ET reactions and provides a natural explanation for a lot of known paradoxes of ET reactions

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