Operator Formulation of Feynman Path Centroid Dynamics for Rotations

An operator formulation of centroid molecular dynamics (CMD) for rotational degrees of freedom is presented. The quasi-density operator concept was introduced by Jang and Voth J. Chem. Phys 111, 2357 (1999) and is used to obtain a phase-space mapping without the need for discretized path integrals. The approach allows the calculation of approximate Kubo-transformed time correlation functions. The particle on a ring is chosen as an illustrative example. Numerical results demonstrate that the proposed approach leads to accurate results when compared with exact diagonalization calculations for linear operators. At very low temperatures, it is found that rotational CMD yields results that are in exact agreement with the quantum dynamics of a spin-1 system.