On the “direct” calculation of thermal rate constants. II. The flux-flux autocorrelation function with absorbing potentials, with application to the O+HCl→OH+Cl reaction
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Issue Date
1997-01-01Author
Thompson, Ward H.
Miller, William H.
Publisher
American Institute of Physics
Type
Article
Article Version
Scholarly/refereed, publisher version
Metadata
Show full item recordAbstract
We present a method for obtaining the thermal rate constant directly (i.e., without first solving the state-to-state reactive scattering problem) from the time integral of the flux-flux autocorrelation function, Cff(t). The quantum mechanical trace involved in calculating Cff(t) is efficiently evaluated by taking advantage of the low rank of the Boltzmannized flux operator. The time propagation is carried out with a Hamiltonian which includes imaginary absorbing potentials in the reactant and product exit channels. These potentials eliminate reflection from the edge of the finite basis and ensure that Cff(t) goes to zero at long times. In addition, the basis can then be contracted to represent a smaller area around the interaction region. We present results of this method applied to the O+HCl reaction using the J-shifting and helicity conserving approximations to include nonzero total angular momentum. The calculated rate constants are compared to experimental and previous theoretical results. Finally, the effect of deuteration (the O+DCl reaction) on the rate constant is examined.
Description
This is the publisher's version, also available electronically from http://scitation.aip.org/content/aip/journal/jcp/106/1/10.1063/1.474109
ISSN
0021-9606Collections
Citation
Thompson, Ward H.; Miller, William H. (1997). "On the “direct” calculation of thermal rate constants. II. The flux-flux autocorrelation function with absorbing potentials, with application to the O+HCl→OH+Cl reaction." The Journal of Chemical Physics, 142(1):142-150. http://dx.doi.org/10.1063/1.474109
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