A five-site model for liquid water and the reproduction of the density anomaly by rigid, nonpolarizable potential functions

TLDR

The study investigates whether simple potential functions can accurately reproduce liquid water density across −37 °C to 100 °C and 1–10 000 atm. Using extensive classical Monte Carlo simulations, the authors optimized a five‑site TIP5P model, adjusting lone‑pair charge positions and sampling over 1 billion configurations to match the density curve shape. The resulting TIP5P model achieves a mean density error of only 0.006 g cm⁻³ over the temperature range, correctly reproduces the 4 °C density maximum, matches the dielectric constant (81.5 ± 1.5 at 25 °C), and maintains ~2 % accuracy across 1–10 000 atm.

Abstract

The ability of simple potential functions to reproduce accurately the density of liquid water from −37 to 100 °C at 1 to 10 000 atm has been further explored. The result is the five-site TIP5P model, which yields significantly improved results; the average error in the density over the 100° temperature range from −37.5 to 62.5 °C at 1 atm is only 0.006 g cm−3. Classical Monte Carlo statistical mechanics calculations have been performed to optimize the parameters, especially the position of the negative charges along the lone-pair directions. Initial calculations with 216 molecules in the NPT ensemble at 1 atm focused on finding a model that reproduced the shape of the liquid density curve as a function of temperature. Calculations performed for 512 molecules with the final TIP5P model demonstrate that the density maximum near 4 °C at 1 atm is reproduced, while high-quality structural and thermodynamic results are maintained. Attainment of high precision for the low-temperature runs required sampling for more than 1 billion Monte Carlo configurations. In addition, the dielectric constant was computed from the response to an applied electric field; the result is 81.5±1.5 at 25 °C and the experimental curve is mirrored from 0–100 °C at 1 atm. The TIP5P model is also found to perform well as a function of pressure; the density of liquid water at 25 °C is reproduced with an average error of ∼2% over the range from 1 to 10 000 atm, and the shift of the temperature of maximum density to lower temperature with increasing pressure is also obtained.