Centroid-based methods for calculating quantum reaction rate constants: Centroid sampling versus centroid dynamics

Abstract

A new method was recently introduced for calculating quantum mechanical rate constants from centroid molecular dynamics (CMD) simulations [E. Geva, Q. Shi, and G. A. Voth, J. Chem. Phys. 115, 9209 (2001)]. This new method is based on a formulation of the reaction rate constant in terms of the position-flux correlation function, which can be approximated in a well defined way via CMD. In the present paper, we consider two different approximated versions of this new method, which enhance its computational feasibility. The first approximation is based on propagating initial states which are sampled from the initial centroid distribution, on the classical potential surface. The second approximation is equivalent to a classical-like calculation of the reaction rate constant on the centroid potential, and has two distinct advantages: (1) it bypasses the problem of inefficient sampling which limits the applicability of the full CMD method at very low temperatures; (2) it has a well defined TST limit which is directly related to path-integral quantum transition state theory (PI-QTST). The approximations are tested on a model consisting of a symmetric double-well bilinearly coupled to a harmonic bath. Both approximations are quite successful in reproducing the results obtained via full CMD, and the second approximation is shown to provide a good estimate to the exact high-friction rate constants at very low temperatures. © 2002 American Institute of Physics.