On the ‘‘direct’’ calculation of thermal rate constants
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Issue Date
1995-03-01Author
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 new approach for the direct (and correct) calculation of thermal rate constantsk(T) (‘‘direct’’ meaning that one avoids having to solve the state‐to‐state reactive scattering problem, and ‘‘correct’’ meaning that the method contains no inherent approximations). The rate constant is obtained from the long time limit of the flux‐position correlation function,C f,s (t), whose calculation is made efficient by taking advantage of the low rank of the flux operator. Specifically, the trace required to obtain C f,s (t) is evaluated by a Lanczos iteration procedure which calculates only the nonzero eigenvalues. The propagation in complex time, t c =t−iℏβ/2, is carried out using a Chebychev expansion. This method is seen to be both accurate and efficient by application to the Eckart barrier, the collinear H+H2reaction, and the three‐dimensional D+H2 (J=0) reaction.
Description
This is the publisher's version, also available electronically from http://scitation.aip.org/content/aip/journal/jcp/102/19/10.1063/1.469053.
ISSN
0021-9606Collections
Citation
Thompson, Ward H.; Miller, William H. (1995). "On the ‘‘direct’’ calculation of thermal rate constants." The Journal of Chemical Physics, 102(19):7409-7417. http://www.dx.doi.org/10.1063/1.469053
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