Relations between thermodynamics, structures, and dynamics for modified water models in their supercooled regimes

• Published in: The Journal of chemical physics Vol. 154; no. 5; pp. 054502 - 54514
• Main Authors: Horstmann, R., Vogel, M.
• Format: Journal Article
• Language: English
• Published: United States 07.02.2021
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/5.0037080

We use molecular dynamics simulations to study relations between thermodymamic, structural, and dynamical properties of TIP4P/2005 water models with systematically reduced partial charges and, thus, weaker hydrogen bonds. Observing a crossing of isochores in the P–T diagram, we show that these water-like models have a readily accessible liquid–liquid critical point (LLCP) associated with a transition between high-density liquid (HDL) and low-density liquid (LDL) forms and determine the dependence of the critical temperature Tc, pressure Pc, and density ρc on the charge-scaling factor from fits to a two-structure equation of states. The results indicate that the water-like models exhibit liquid polyamorphism in a wide range of interaction parameters. Considering elongated systems, we observe a decomposition into extended and stable HDL-like and LDL-like regions at appropriate pressures and low temperatures and analyze the respective structural and dynamical properties. We show that the diverse local order results in very different correlation times of local dynamics, while the fragility is hardly changed. The results yield insights into the origin of a dynamical crossover, which is observed when lowering the temperature along isobars and was previously interpreted in terms of a fragile-to-strong transition. Our findings imply that the effect does not involve two liquid phases with an exceptionally large difference of the fragility but rather a high temperature dependence near the LLCP results from a rapid conversion from HDL-like environments with faster dynamics to LDL-like ones with slower dynamics.