Abstract
Abstract The quantum dynamics of a proton (PT) reaction in a polar solvent, treated as continuum, is considered taking as an example the PT process Flu − + HFlu → HFlu + Flu − 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 ( K H ) and the H D isotope effect cannot be consistently described within the present two-level scheme.
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