Thermodynamic perturbation theory for rotational degrees of freedom. Application to the Mercedes-Benz water model

摘要

We developed a fast theory for studying how the rotational temperature (and rotational degrees of freedom) affects the properties of a simple model of liquid water. Wertheim's Thermodynamic perturbation theory (TPT) for associative liquids was applied to the Mercedes-Benz (MB) model. 2D MB model is one of the simplest models of water. The MB particles are modelled as Lennard-Jones disks with three hydrogen bonding arms arranged symmetrically as in the MB logo. We previously applied TPT to this model. We found that the physical properties were well reproduced by the theory. Here, we propose an modified version of the thermodynamic perturbation theory in which it is possible to treat rotational degrees of freedom by using different averaging then used before. By holding translational or rotational temperature constant and varying the other one, we investigate their effect on the properties of the simple water model and how well TPT reproduces computer simulation results. The new results are in good agreement with the Monte Carlo values of the pressure and energy. We also investigated how rotational temperature affects thermodynamic properties of the critical point. A major advantage of these theories is that they require orders of magnitude less computer time than the Monte Carlo simulations. (C) 2021 Elsevier B.V. All rights reserved.