Microscopic derivation of coarse-grained, energy-conserving generalized Langevin dynamics.

Properly simulating nonequilibrium phenomena such as thermal transport and shock wave propagation in complex condensed matter systems require the conservation of system's internal energy. This precludes the application of the coarse-grained (CG) generalized Langevin equation (GLE) dynamics due to the presence of dissipative interactions. Attempts to address this issue have been pursued both phenomenologically and from entropy-based first principles for dissipative particle dynamics (DPD, a Markovian variant of the CG GLE dynamics) by introducing an energy conserving extension of DPD (DPD-E). We present here a rigorous microscopic derivation of two energy conserving variants of the CG GLE dynamics by extending the CG equations of motion to include the GLE for certain internal energy observables of the microscopic system. We consider two choices of such observables: the total internal energy and a set of internal energies of the CG particles. The derivation is performed using the Mori-Zwanzig projection operator method in the Heisenberg picture for time evolution of thermodynamic expectations and the recently introduced interpretation of the Zwanzig projection operator [S. Izvekov, J. Chem. Phys. 146(12), 124109 (2017)] which allows an exact calculation of the memory and projected terms. We begin with equilibrium conditions and show that the GLE dynamics for the internal energy observables is purely dissipative. Our extension of the GLE dynamics to quasiequilibrium conditions (necessary to observe heat transport) is based on the generalized canonical ensemble approach and transport equation using the nonequilibrium statistical operator (NSO) method. We derive closed microscopic expressions for conductive heat transfer coefficients in the limit of neglecting dissipation in heat transfer and in the lowest order of deviation from equilibrium. After employing the Markov approximation, we compare the equations of motion to the published DPD-E equations. Our equations contain additional energy transfer terms not reported in the previous works. Additionally, we show that, despite neglecting dissipative processes in heat transport, the heat transfer coefficients and random force are related in a way reminiscent of the fluctuation-dissipation relation. The formalism presented here is sufficiently general for the rigorous formulation of the GLE dynamics for arbitrary microscopic phase space observables as well as sampling different microscopic ensembles in CG simulations.