Path integral Brownian chain molecular dynamics: A simple approximation of quantum vibrational dynamics.

Abstract

An approximate approach to quantum vibrational dynamics, "Brownian chain molecular dynamics (BCMD)," is proposed to alleviate the chain resonance and curvature problems in the imaginary time-based path integral (PI) simulation. Here the non-centroid velocity is randomized at each step when solving the equation of motion of path integral molecular dynamics. This leads to a combination of the Newton equation and the overdamped Langevin equation for the centroid and non-centroid variables, respectively. BCMD shares the basic properties of other PI approaches such as centroid and ring polymer molecular dynamics: It gives the correct Kubo-transformed correlation function at short times, conserves the time symmetry, has the correct high-temperature/classical limits, gives exactly the position and velocity autocorrelations of harmonic oscillator systems, and does not have the zero-point leakage problem. Numerical tests were done on simple molecular models and liquid water. On-the-fly ab initio BCMD simulations were performed for the protonated water cluster, , and its isotopologue, .