Equipartitioning of Molecular Degrees of Freedom in MD Simulations of Gaseous Systems via an Advanced Thermostatization Strategy.

This work introduces a dedicated thermostatization strategy for molecular dynamics simulations of gaseous systems. The proposed thermostat is based on the stochastic canonical velocity rescaling approach by Bussi and co-workers and is capable of ensuring an equal distribution of the kinetic energy among the translational, rotational, and vibrational degrees of freedom. The outlined framework ensures the correct treatment of the kinetic energy in gaseous systems, which is typically not the case in standard approaches due to the limited number of collisions between particles associated with a large free mean path. Additionally, an efficient strategy to effectively correct for intramolecular contributions to the virial in quantum mechanical simulations is presented. The equipartitioning thermostat was successfully tested by the determination of pV diagrams for carbon dioxide and methane at the density functional tight binding level of theory. The results unequivocally demonstrate that the equipartitioning thermostat can effectively achieve an equal distribution of the kinetic energy among the different degrees of freedom, thereby ensuring correct pressure in gaseous systems. Furthermore, RDF calculations show the capability of the proposed method to accurately depict the structure of gaseous systems, as well as enable an adequate treatment of gas molecules under confinement, as exemplified by an MD simulation of (CO₂)₅₀@MOF-5.