The Interplay between Memory and Potentials of Mean Force: A Discussion on the Structure of Equations of Motion for Coarse Grained Observables

Abstract: The underdamped, non-linear, generalized Langevin equation is widely used to model coarse-grained dynamics of soft and biological materials. By means of a projection operator formalism, we show under which approximations this equation can be obtained from the Hamiltonian dynamics of the underlying microscopic system and in which cases it makes sense to introduce a potential of mean force. We discuss shortcomings of previous derivations presented in the literature and demonstrate the implications of our derivation for the structure of memory terms and their connection to generalized fluctuation-dissipation relations. We show, in particular, that the widely used, simple structure which contains a potential of mean force, a memory term which is linear in the observable, and a fluctuating force which is related to the memory term by a fluctuation-dissipation relation, is neither exact nor can it, in general, be derived as a controlled approximation to the exact dynamics.