Comparison of different exact generalized Langevin equations with a non-linear potential of mean force and an observable-dependent mass and friction

Abstract

The Mori-Zwanzig projection formalism constitutes a powerful and robust framework for deriving equations of motion in terms of generalized Langevin equations (GLEs) for an arbitrary observable using evolution and projection operators. Based on this framework, we analyze the properties of four distinct GLEs for a scalar observable including a Markovian force derived from a generally non-linear potential, a non-Markovian friction force, and an orthogonal force, commonly interpreted as a random force. While all four GLEs are exact, they differ in the memory friction kernel, which may either be dependent or independent of the observable, and by the potential, which may either include or exclude the effective kinetic energy of the observable. Inclusion of the kinetic energy in the potential is advantageous for observables whose velocity satisfies Wick's theorem, since this reproduces the correct distribution of the observable and its velocity even without contributions from the friction force and the orthogonal force.