Boundary condition independence of molecular dynamics simulations of planar elongational flow

Abstract

The simulation of liquid systems in a nonequilibrium steady state under planar elongational flow (PEF) for indefinite time is possible only with the use of the so-called Kraynik-Reinelt (KR) periodic boundary conditions (PBCs) on the simulation cell. These conditions admit a vast range of implementation parameters, which regulate how the unit lattice is deformed under elongation and periodically remapped onto itself. Clearly, nonequilibrium properties of homogeneous systems in a steady state have to be independent of the boundary conditions imposed on the unit cell. In order to confirm the independence of measurable properties of a system under PEF from the particular set of periodic boundary conditions, we compute the Lyapunov spectra, apply the conjugate pairing rule, and carefully analyze the so-called unpaired exponents for an atomic fluid of various sizes and state points. We further compute the elongational viscosity for various implementations of boundary conditions. All our results confirm the independence from KR PBCs for the dynamics of phase-space trajectories and for the transport coefficients.