TY - JOUR

T1 - Quantum initial conditions in quasi-classical trajectory calculations

AU - Bowman, Joel M.

AU - Kuppermann, Aron

AU - Schatz, George C.

N1 - Funding Information:
* This work was supported in part by the United States Atomic Energy Commission, Report Code No. CALT.-767P4-101. ** Work performed in partial fulfilment of the requirements for the Ph.D. Degree in Chemistry at the California Institute of Technology. t Contribution No. 4596.
Copyright:
Copyright 2014 Elsevier B.V., All rights reserved.

PY - 1973

Y1 - 1973

N2 - The quantum distribution of initial conditions suggested recently by Careless and Hyatt as a means of "phase-averaging" classical trajectories is shown to lead to reaction probabilities which depend on the initial distance between the reagents even when this distance is sufficiently large for the corresponding interaction energy to vanish. We used that distribution to calculate reaction probabilities for the collinear H + H2 exchange reaction on a potential energy surface for which quasi-classical and exact quantum results had been previously obtained. The dependence of the resulting reaction probabilities on the arbitrarily chosen value of the initial atom-molecule separation was substantial. We conclude that the use of such quantum distributions for initial conditions is physically unacceptable.

AB - The quantum distribution of initial conditions suggested recently by Careless and Hyatt as a means of "phase-averaging" classical trajectories is shown to lead to reaction probabilities which depend on the initial distance between the reagents even when this distance is sufficiently large for the corresponding interaction energy to vanish. We used that distribution to calculate reaction probabilities for the collinear H + H2 exchange reaction on a potential energy surface for which quasi-classical and exact quantum results had been previously obtained. The dependence of the resulting reaction probabilities on the arbitrarily chosen value of the initial atom-molecule separation was substantial. We conclude that the use of such quantum distributions for initial conditions is physically unacceptable.

UR - http://www.scopus.com/inward/record.url?scp=33750063341&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33750063341&partnerID=8YFLogxK

U2 - 10.1016/0009-2614(73)87052-6

DO - 10.1016/0009-2614(73)87052-6

M3 - Article

AN - SCOPUS:33750063341

VL - 19

SP - 21

EP - 25

JO - Chemical Physics Letters

JF - Chemical Physics Letters

SN - 0009-2614

IS - 1

ER -