Nonequilibrium solvation effects on reaction rates for model SN2 reactions in water

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Abstract
Molecular dynamics (MD) simulations of the model SN2 reaction Cl−+CH3Cl→ClCH3+Cl− in water, and variants thereof, are presented. The resulting transmission coefficients κ, that measure the deviations of the rates from the transition state theory (TST) rate predictions due to solvent‐induced recrossings, are used to assess the validity of the generalized Langevin equation (GLE)‐based Grote–Hynes (GH) theory. The GH predictions are found to agree with the MD results to within the error bars of the calculations for each of the 12 cases examined. This agreement extends from the nonadiabatic regime, where solvent molecule motions are unimportant and κ is determined by static solvent configurations at the transition state, into the polarization caging regime, where solvent motion is critical in determining κ. In contrast, the Kramers theory predictions for κ fall well below the simulation results. The friction kernel in the GLE used to evaluate the GH κ values is determined, from MD simulation, by a fixed‐particle time correlation function of the force at the transition state. When this is expressed as a (Fourier) friction spectrum in frequency, marked similarities to the pure solvent spectrum are observed, and are used to identify the water solvent motions that determine the transmission coefficient κ. The deviations of κ from unity, the TST value, are dominated by solvent motions (translational and reorientational) which on the time scale of the recrossings are essentially static configurations. The deviations from the frozen solvent, nonadiabatic limit values κNA are dominated by the hinderd rotations (librations). Finally, the underlying assumptions of the GLE and the GH theory are discussed within the context of the simulation results.