1887
banner image
No data available.
Please log in to see this content.
You have no subscription access to this content.
No metrics data to plot.
The attempt to load metrics for this article has failed.
The attempt to plot a graph for these metrics has failed.
A harmonic transition state approximation for the duration of reactive events in complex molecular rearrangements
Rent:
Rent this article for
USD
10.1063/1.3459058
/content/aip/journal/jcp/133/3/10.1063/1.3459058
http://aip.metastore.ingenta.com/content/aip/journal/jcp/133/3/10.1063/1.3459058
View: Figures

Figures

Image of FIG. 1.
FIG. 1.

Left: a long trajectory occasionally enters the transition region T between two basins of attraction, A and B, corresponding to the reactants and products of a chemical reaction. A transition path from A to B enters T from A and exits to B (bold segments of the trajectory). The corresponding transit time is the time interval between the moment the transition region is entered from A and the moment the trajectory finally arrives at B. Right: a reactive trajectory traveling between A and B may recross an intermediate dividing surface located inside the transition region T.

Image of FIG. 2.
FIG. 2.

A one dimensional potential , with a maximum value in the transition region .

Image of FIG. 3.
FIG. 3.

Distribution of transit times computed numerically for the case of a parabolic barrier (solid line) and compared with Eq. (25) (dashed lines) for (a) and (b) .

Image of FIG. 4.
FIG. 4.

(a) Contour plot of the potential of Eq. (27) with , , , and representative transition paths in this potential. The transition region is shaded. (b) Histogram of transit times obtained from simulations, compared with Eq. (25), where was estimated as the free energy barrier (solid line) and using Eq. (30) (dashed line). (c) Potentials profiles [ plotted vs ] traversed by the transition paths from (a). The thick line shows the potential .

Image of FIG. 5.
FIG. 5.

(a) Contour plot of the potential of Eq. (27) with , , , and representative transition paths in this potential. The transition region is shaded. (b) Histogram of transit times obtained from simulations, compared with Eq. (25), where was estimated as the free energy barrier (solid line) and using Eq. (30) (dashed line). (c) Potentials profiles [ plotted vs ] traversed by the transition paths from (a). The thick line shows the potential .

Image of FIG. 6.
FIG. 6.

(a) Contour plot of the potential of Eq. (27) with , , , and representative transition paths in this potential. The transition region is shaded. (b) Histogram of transit times obtained from simulations, compared with Eq. (25), where was estimated as the free energy barrier (solid line) and using Eq. (30) (dashed line). (c) Potential profiles [ plotted vs ] traversed by the transition paths from Fig. 4(a). The thick line shows the potential .

Image of FIG. 7.
FIG. 7.

Same data as in Fig. 4(b) but plotted on a logarithmic scale to show the exponential behavior of the distribution at long times.

Loading

Article metrics loading...

/content/aip/journal/jcp/133/3/10.1063/1.3459058
2010-07-20
2014-04-17
Loading

Full text loading...

This is a required field
Please enter a valid email address
752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: A harmonic transition state approximation for the duration of reactive events in complex molecular rearrangements
http://aip.metastore.ingenta.com/content/aip/journal/jcp/133/3/10.1063/1.3459058
10.1063/1.3459058
SEARCH_EXPAND_ITEM