A mixed quantum classical rate theory (MQCLT) is applied to the collinear h
ydrogen exchange reaction on the LSTH and PK II potential energy surfaces.
Classical trajectories are combined with a numerically exact quantum Monte
Carlo evaluation of the thermal flux operator to compute the thermal reacti
on rate. The MQCLT results are compared to quantum transition state theory
(QTST) and centroid rate theory computations. The computed rates are found
to bound the exact results from above for temperatures ranging from T=200 K
to T=1000 K. As in previous studies, the mixed quantum classical theory gi
ves better agreement with numerically exact computations, than the QTST com
putations, while the added numerical effort is not prohibitive. The MQCLT r
ate is almost exact at high temperature. At T=200 K it is a factor of 2.8 (
2.0) greater than the exact rate on the LSTH (PK II) potential energy surfa
ce, a significant improvement over the QTST overestimate of 3.7 (3.4). The
mixed quantum classical results are comparable in accuracy to the centroid
theory computations, except that the centroid theory is always lower than t
he exact result while MQCLT is always higher. (C) 2001 American Institute o
f Physics.