Schematic illustration of the Azzouz–Borgis model for proton transfer between phenol (AH) and trimethylamine (B) in liquid methyl chloride. Adapted from Fig. 1 of Kim and Hammes-Schiffer (Ref. 2).
Free energy curves for the Azzouz–Borgis model as a function of the proton transfer distance , obtained from simulations in which only the transferring proton (deuteron) was quantized. The classical free energy curve is also shown for comparison.
Centroid probability distributions as a function of the proton transfer distance , obtained from fully quantized RPMD simulations of the AH–B (AD–B) reactant complex. The classical distribution is also shown for comparison.
Time-dependent transmission coefficients , obtained from (a) partially quantized and (b) fully quantized RPMD simulations of proton and deuteron transfer using the proton transfer distance as the reaction coordinate.
The centroids of two typical RPMD proton transfer trajectories exhibiting recrossing dynamics, superimposed on contours of the two-dimensional free energy surface and plotted as a function of the mass-scaled coordinates and . The open and shaded circles indicate the starting and ending points of each trajectory. The free energy contour spacing is .
As in Fig. 5, but for deuteron transfer, and with a contour spacing of .
Time-dependence of the proton transfer distance for the trajectories shown in Fig. 5. The horizontal dotted line is at .
As in Fig. 7, but for deuteron transfer.
Time dependence of the collective solvent coordinate in Eq. (61) for the proton transfer trajectories shown in Fig. 5. The illustrations on the right show the instantaneous potential experienced by the transferring proton (solid) and the corresponding ground adiabatic wave function (dashed) at three different points along each trajectory.
As in Fig. 9, but for deuteron transfer.
Results of previous studies of the Azzouz–Borgis model with the parameterization of Hammes-Schiffer and Tully. Computed rate coefficients are given in units of .
Standard parameters for the Azzouz–Borgis model, as used in Refs. 1, 2, 5, and 12.
Comparison of the present results with those of previous studies of the Azzouz–Borgis model (see also Table I). Computed rate coefficients are given in units of .
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