The effect of intra-molecular bonds on the liquid–liquid critical point in modified-WAC models

Abstract

To obtain a better understanding of liquid–liquid critical points (LLCPs) in one-component liquids, we extend the modified-WAC model by E. Lascaris, Phys. Rev. Lett. 116, 125701 (2016) which is known to have a LLCP. The original WAC model is a model for silica (SiO2) and consists of a mixture of non-bonded Si and O ions. By adding explicit intra-molecular Si–O bonds to the model, we are able to study how several parameters (Si–O bond length, O–Si–O angle, and bond stiffness) affect the existence and location of the LLCP. We find that for this model, only the Si–O bond length has a strong effect on the LLCP, while the bond angle and bond stiffness have no significant effect on the LLCP. An analysis of the relevant coordination numbers indicates that increasing the bond length decreases the ratio RSi/O of additional Si ions per additional O ion in the first coordination shell of the Si, which causes the LLCP to move to higher, more accessible temperatures. The behavior of the RSi/O parameter shows a strong correlation with the behavior of the LLCP and might be a useful tool to determine if a LLCP exists at low, hard-to-reach temperatures in other models.