Dynamics of proton transfer reactions in polar solvent in the non-adiabatic two-state approximation: Test calculations for carbon-carbon reaction centre

M. V. Basilevsky, M. V. Vener, G. V. Davidovich, A. V. Soudackov

Research output: Contribution to journalArticlepeer-review

Abstract

The quantum dynamics of a proton transfer (PT) reaction in a polar solvent, treated as continuum, is considered taking as an example the PT process Flu- + HFlu → HFlu + Flu- (a) in ether, where FluH means fluorene. Using the model three-dimensional free-energy surface (FES) derived from quantum-chemical SCRF calculations, the dynamical description is reduced to a two-level stochastic Liouville equation in the two-dimensional subspace spanned by the solute vibrational mode (representing a relative motion of heavy atoms constituting the PT reaction centre) and a solvent collective coordinate. The two quantum states involved in a reactive event are a pair of lowest proton levels obtained by means of quantum-mechanical averaging the basic three-dimensional FES. The new methodology of a direct evaluation of the coupling matrix element is elaborated. The rate calculation involves a treatment of extremely small ( ∼ 10-5-10-10) transmission factors for which two different approximate non-adiabatic approaches are tested. The whole variety of experimental data on reaction (a) involving both the absolute values of the rate constant (KH) and the H/D isotope effect cannot be consistently described within the present two-level scheme.

Original languageEnglish (US)
Pages (from-to)267-282
Number of pages16
JournalChemical Physics
Volume208
Issue number2
DOIs
StatePublished - Aug 1 1996

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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