Nonequilibrium induced by reservoirs: Physico-mathematical models and numerical tests

TL;DR

This paper evaluates a linear reservoir coupling model for open molecular systems under nonequilibrium conditions, using molecular dynamics simulations to test its applicability and proposing an extension to include nonlinear effects.

Contribution

It tests the linear coupling model in nonequilibrium scenarios and suggests an extension to incorporate nonlinear reservoir interactions.

Findings

Linear coupling model is effective within certain nonequilibrium regimes.

Density profiles show deviations indicating nonlinear effects.

Proposed model extension aims to better capture feedback mechanisms.

Abstract

In a recently proposed computational model of open molecular systems out of equilibrium [Ebrahimi Viand et al. J.Chem.Phys. 153, 101102 (2020)], the action of different reservoirs enters as a linear sum into the Liouville-type evolution equations for the open system's statistics. The linearity of the coupling is common to different mathematical models of open systems and essentially relies on neglecting the feedback of the system onto the reservoir due to their interaction. In this paper, we test the range of applicability of the computational model with a linear coupling to two different reservoirs, which induces a nonequilibrium situation. To this end, we studied the density profiles of Lennard-Jones liquids in large thermal gradients using nonequilibrium molecular dynamics simulations with open boundaries. We put in perspective the formulation of an extension of the mathematical model that can account for nonlinear effects.