Simulating a flexible water model as rigid: Best practices and lessons learned.

Abstract

Two ways to create rigid versions of flexible models are explored. The rigid model can assume the Model's Geometry (MG) as if the molecule is not interacting with any other molecules or the ensemble averaged geometry (EG) under a particular thermodynamic condition. Although the MG model is more straightforward to create, it leads to relatively poor performance. The EG model behaves similarly to the corresponding flexible model (the FL model) and, in some cases, agrees even better with experiments. While the difference between the EG and the FL models is mostly a result of flexibility, the MG and EG models have different dipole moments as a result of an effective induction in the condensed phase. For the three water models studied, the property that shows the most difference is the temperature dependence of density. The MG version of the water model by adaptive force matching for ice and liquid does not possess a temperature of maximum density, which is attributed to a downshift of the putative liquid-liquid phase transition line, leading to the hypothesized second critical point of liquid water to manifest at negative pressure. A new three-phase coexistence method for determining the melting temperature of ice is also presented.