Classical cumulant dynamics for statistical chemical physics

Abstract

We developed classical cumulant dynamics for statistical mechanics in order to evaluate thermal equilibrium properties of a given system. The equations of motion (EOMs) for momentum and position were formulated together with those for second-order cumulant variables, which are functions of second-order moments. From the Kramers equation, and simplified EOMs were obtained by assuming a stationary state limit. The present method combined with the umbrella integration method was applied to evaluate free energy surface of a seven-particle Morse cluster. With low computational costs, the present approach gave almost equivalent free energy barrier those by conventional classical molecular dynamics.

Keywords:

• Statistical mechanics
• molecular dynamics
• cumulant expansion
• Morse cluster