Accuracy limit of non-polarizable four-point water models: TIP4P/2005 vs OPC. Should water models reproduce the experimental dielectric constant?

• Published in: The Journal of chemical physics Vol. 161; no. 4
• Main Authors: Sedano, L. F., Blazquez, S., Vega, C.
• Format: Journal Article
• Language: English
• Published: United States American Institute of Physics 28.07.2024
• Subjects: Compressibility; Critical temperature; Density; Dielectric strength; Dipole moments; Electric fields; Electrolytes; Equations of state; Fluid dynamics; Melt temperature; Performance evaluation; Permittivity; Phase diagrams; Physical simulation; Potential energy; Temperature; Transport properties
• ISSN: 0021-9606; 1089-7690; 1089-7690
• DOI: 10.1063/5.0211871

The last generation of four center non-polarizable models of water can be divided into two groups: those reproducing the dielectric constant of water, as OPC, and those significantly underestimating its value, as TIP4P/2005. To evaluate the global performance of OPC and TIP4P/2005, we shall follow the test proposed by Vega and Abascal in 2011 evaluating about 40 properties to fairly address this comparison. The liquid–vapor and liquid–solid equilibria are computed, as well as the heat capacities, isothermal compressibilities, surface tensions, densities of different ice polymorphs, the density maximum, equations of state at high pressures, and transport properties. General aspects of the phase diagram are considered by comparing the ratios of different temperatures (namely, the temperature of maximum density, the melting temperature of hexagonal ice, and the critical temperature). The final scores are 7.2 for TIP4P/2005 and 6.3 for OPC. The results of this work strongly suggest that we have reached the limit of what can be achieved with non-polarizable models of water and that the attempt to reproduce the experimental dielectric constant deteriorates the global performance of the water force field. The reason is that the dielectric constant depends on two surfaces (potential energy and dipole moment surfaces), whereas in the absence of an electric field, all properties can be determined simply from just one surface (the potential energy surface). The consequences of the choice of the water model in the modeling of electrolytes in water are also discussed.