Quantum reaction rate from higher derivatives of the thermal flux-flux autocorrelation function at time zero.
A quantum theory of thermal reaction rates is presented which may be viewed as an extension of the recently developed "quantum instanton" (QI) model [W. H. Miller, Y. Zhao, M. Ceotto, and S. Yang, J. Chem. Phys. 119, 1329 (2003)]. It is based on using higher derivatives of the flux-flux autocorrelation function C(t) (as given by Miller, Schwartz, and Tromp) at t=0 to construct a short time approximation for C(t). Tests of this theory on 1d and collinear reactions, both symmetric and asymmetric, show it to be more accurate than the original QI model, giving rate constants to approximately 5% for a wide range of temperature.
Ceotto
Michele
M
Department of Chemistry and Kenneth S. Pitzer Center for Theoretical Chemistry, University of California-Berkeley, Berkeley, CA 94720, USA.
Yang
Sandy
S
Miller
William H
WH