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Chemical reaction rates and solvent friction

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Abstract

The role of the dynamic solvent friction in influencing the rates of chemical reactions in solution is described. Features considered include (a) the bias of the reaction coordinate toward a direction of lesser friction in the diffusive limit, (b) the importance of frequency-dependent friction in atom transfers, tunneling reactions and isomerizations, (c) the dynamic nonequilibrium solvation in charge transfers which leads to a polar solvent molecule reorientation time dependence for the rate, and (d)the importance of internal degrees of freedom in the location of the Kramers turnover for isomerizations.

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  1. Department of Chemistry, University of Colorado, 80309, Boulder, Colorado

    James T. Hynes

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  1. James T. Hynes
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Hynes, J.T. Chemical reaction rates and solvent friction. J Stat Phys 42, 149–168 (1986). https://doi.org/10.1007/BF01010844

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