Effects of thermostats/barostats on physical properties of liquids by molecular dynamics simulations

Thermostats/barostats that maintain temperature/pressure as constant (on average) in molecular dynamics (MD) simulations are essential for simulating isothermal-isochoric (NVT) or isothermal -isobaric (NPT) systems. In order to simulate accurate physical properties, thermostats/barostats need not only sample a correct NVT/NPT ensemble but also minimally disturb the particles' (Newtonian) dynamics. In other words, the NVT/NPT simulations need to yield accurate physical properties (dynamics properties included, e.g. diffusivity and viscosity) and also their fluctuations. However, few studies have studied in-depth the effects of thermostats/barostats on a comprehensively wide range of simulated properties. In this work, commonly used thermostats, e.g. Andersen, stochastic dynamics (SD), Berendsen, V-rescale and Nose-Hoover thermostats, and barostats, e.g. Berendsen and Parrinello-Rahman barostats, with different coupling strengths were studied to see whether they can yield accurate simulated properties and fluctuations. The theoretical values of physical properties' fluctuations were calculated via statistical mechanics to provide a comparison benchmark for MD simulations. Particularly, the accuracy of thermostats was studied in the context of NPT or non-equilibrium molecular dynamics (NEMD) simulations, which has long been overlooked. Berendsen thermostat/barostat sup-presses the fluctuations of energy/volume (due to the exponential decay of deviation of the simulated temperature/pressure from the target value) and yields inaccurate simulated properties. In addition, Andersen and SD thermostats perturb the particles' dynamics so violently (due to the random component in the algorithm) that they fail to accurately simulate dynamics properties. Overall, Nose-Hoover/V-rescale thermostat, and Parrinello-Rahman barostat with moderate coupling strength are recommended for common NVT/NPT production simulations. NPT or NEMD simulations would require more efficient (or stronger coupling) thermostats than NVT equilibrium molecular dynamics (EMD) to maintain the simu-lated temperature close to the target. (c) 2022 Elsevier B.V. All rights reserved.

Automated summary

The choice of thermostats/barostats has a significant impact on the accuracy of simulated properties in molecular dynamics simulations. Nose-Hoover/V-rescale thermostat and Parrinello-Rahman barostat with moderate coupling strength are recommended for common NVT/NPT production simulations.