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.
Extended spin-boson model for nonadiabatic hydrogen tunneling in the condensed phase
Rent:
Rent this article for
USD
10.1063/1.2354500
/content/aip/journal/jcp/125/14/10.1063/1.2354500
http://aip.metastore.ingenta.com/content/aip/journal/jcp/125/14/10.1063/1.2354500
View: Figures

Figures

Image of FIG. 1.
FIG. 1.

Schematic picture of a general hydrogen tunneling system. The double well potential energy curves are functions of the hydrogen coordinate , and the lowest two adiabatic hydrogen vibrational states are depicted for each hydrogen potential energy curve. Reorganization of the bath environment alters the relative energies of the wells of the hydrogen potential energy curves. Hydrogen tunneling is allowed for the symmetric double well potential. Increasing the donor-acceptor distance increases the barrier height and width, thereby decreasing the tunneling splitting between the adiabatic hydrogen vibrational states. In the diabatic representation, the bath reorganization leads to degeneracy of the reactant and product diabatic states, and the nonadiabatic coupling between these states decreases as the donor-acceptor distance increases.

Image of FIG. 2.
FIG. 2.

Contour plots of the reactant and product potential energy surfaces as functions of the donor-acceptor coordinate and a bath mode coordinate . The surfaces are shown for systems with (a) uncoupled donor-acceptor and bath coordinates and (b) coupled donor-acceptor and bath coordinates. Note that the minima of the potential energy surfaces are not affected by the coupling between the coordinates.

Image of FIG. 3.
FIG. 3.

Schematic diagram of the model for hydrogen tunneling. The three subsystems are the two-level system (TLS) with splitting , the donor-acceptor mode with mass and frequency , and the bath consisting of modes with masses and frequencies . The subsystems are coupled through the coupling constants , , and .

Image of FIG. 4.
FIG. 4.

Probability flux correlation function in the strong solvation regime with and . The friction constants corresponding to the coupling between the donor-acceptor mode and the bath are (dashed line) and (solid line). The donor-acceptor mode frequency is and the temperature is .

Image of FIG. 5.
FIG. 5.

Dependence of the rate on in the strong solvation regime with and . The friction constants corresponding to the coupling between the donor-acceptor mode and the bath are (dashed line) and (solid line). The temperature is and the donor-acceptor mode frequency is varied.

Image of FIG. 6.
FIG. 6.

Dependence of the rate constant on the energy bias in the strong solvation regime with , , and . The dashed, dot-dashed, and solid lines correspond to , , and , respectively. The thin vertical line separates the inverted regime (left) and the normal regime (right) for .

Image of FIG. 7.
FIG. 7.

Dependence of the rate on in the strong solvation regime with , , and . The dashed and solid lines correspond to (inverted regime) and (normal regime), respectively.

Image of FIG. 8.
FIG. 8.

Probability flux correlation function in the weak solvation regime with and . The friction constants corresponding to the coupling between the donor-acceptor mode and the bath are (a) and (b) . The donor-acceptor mode frequency is and the temperature is .

Image of FIG. 9.
FIG. 9.

Dependence of the rate constant on the energy bias in the weak solvation regime with . The friction constants corresponding to the coupling between the donor-acceptor mode and the bath are (oscillatory thin line) and (smooth thick line). The donor-acceptor mode frequency is and the temperature is .

Image of FIG. 10.
FIG. 10.

Temperature dependence of the rate constant in the weak solvation regime for the case of a low donor-acceptor mode frequency . The parameters for this model system are , , , , and .

Image of FIG. 11.
FIG. 11.

Temperature dependence of the rate constant in the weak solvation regime for the case of a high donor-acceptor mode frequency . The parameters that are the same for both model systems are , , and . The other parameters are (a) , , , , and and (b) , , , , and .

Loading

Article metrics loading...

/content/aip/journal/jcp/125/14/10.1063/1.2354500
2006-10-13
2014-04-16
Loading

Full text loading...

This is a required field
Please enter a valid email address
752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Extended spin-boson model for nonadiabatic hydrogen tunneling in the condensed phase
http://aip.metastore.ingenta.com/content/aip/journal/jcp/125/14/10.1063/1.2354500
10.1063/1.2354500
SEARCH_EXPAND_ITEM