Competition and interplay of various intermolecular interactions in ultrafast excited-state proton and electron transfer reactions

Michael G. Kuzmin*, Irina V. Soboleva, Vladimir L. Ivanov, Elizabeth Ann Gould, Dan Huppert, Kyril M. Solntsev

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

11 Scopus citations

Abstract

The main features of the photoinduced kinetics of both ultrafast excited-state proton and electron transfer reactions that occur in the picosecond (ps) and femtosecond (fs) time domains are compared. Proton transfer (PT) reaction kinetics can be described in terms of several discrete values of rate coefficients in the form of polyexponential functions where each value of the rate coefficient can be attributed to a definite physical behavior of the reaction mechanism. In contrast, electron transfer (ET) reaction kinetics requires a consideration of a continuous distribution of rate coefficients. This difference can be related to structure of the ground-state reactant pairs for each reaction. Excited-state ET can occur at various configurations of reactant molecules and its rate reflects the fluctuations of the distances and orientations of these molecules. In contrast, excited-state PT requires preliminary formation of a ground-state H-bonded complex with definite structure where the reaction occurs after photoexcitation.

Original languageEnglish
Pages (from-to)2444-2453
Number of pages10
JournalJournal of Physical Chemistry B
Volume119
Issue number6
DOIs
StatePublished - 12 Feb 2015

Funding

FundersFunder number
Israel Science Foundation
National Science FoundationCHE-1213047
National Science Foundation1213047

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