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Proton transfer in a polar solvent from ring polymer reaction rate theory
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10.1063/1.2883593
/content/aip/journal/jcp/128/14/10.1063/1.2883593
http://aip.metastore.ingenta.com/content/aip/journal/jcp/128/14/10.1063/1.2883593

Figures

Image of FIG. 1.
FIG. 1.

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).

Image of FIG. 2.
FIG. 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.

Image of FIG. 3.
FIG. 3.

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.

Image of FIG. 4.
FIG. 4.

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.

Image of FIG. 5.
FIG. 5.

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 .

Image of FIG. 6.
FIG. 6.

As in Fig. 5, but for deuteron transfer, and with a contour spacing of .

Image of FIG. 7.
FIG. 7.

Time-dependence of the proton transfer distance for the trajectories shown in Fig. 5. The horizontal dotted line is at .

Image of FIG. 8.
FIG. 8.

As in Fig. 7, but for deuteron transfer.

Image of FIG. 9.
FIG. 9.

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.

Image of FIG. 10.
FIG. 10.

As in Fig. 9, but for deuteron transfer.

Tables

Generic image for table
Table I.

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 .

Generic image for table
Table II.

Standard parameters for the Azzouz–Borgis model, as used in Refs. 1, 2, 5, and 12.

Generic image for table
Table III.

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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/content/aip/journal/jcp/128/14/10.1063/1.2883593
2008-04-09
2014-04-18
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Proton transfer in a polar solvent from ring polymer reaction rate theory
http://aip.metastore.ingenta.com/content/aip/journal/jcp/128/14/10.1063/1.2883593
10.1063/1.2883593
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