ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
A new formulation of quantum transition state theory for adiabatic reactions is proposed. It is based on the flux–flux correlation function of Miller, Schwartz, and Tromp, and calculation of a rate constant requires only the calculation of this correlation function and its second derivative at zero time. The theory is tested for a one-dimensional Eckart barrier and a parabolic barrier linearly coupled to a harmonic oscillator. This quantum transition state theory is exact for a one-dimensional parabolic barrier, is accurate for the model problems studied even under highly quantum conditions, and in the classical limit ((h-dash-bar)→0) becomes classical transition state theory. An analytic continuation procedure for calculating corrections to the transition state theory is discussed.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.467318
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