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 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.
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22 May 2000
Research Article|
May 22 2000
A five-site model for liquid water and the reproduction of the density anomaly by rigid, nonpolarizable potential functions
Michael W. Mahoney;
Michael W. Mahoney
Department of Physics, Yale University, New Haven, Connecticut 06520
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William L. Jorgensen
William L. Jorgensen
Department of Chemistry, Yale University, New Haven, Connecticut 06520
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J. Chem. Phys. 112, 8910–8922 (2000)
Article history
Received:
October 27 1999
Accepted:
February 29 2000
Citation
Michael W. Mahoney, William L. Jorgensen; A five-site model for liquid water and the reproduction of the density anomaly by rigid, nonpolarizable potential functions. J. Chem. Phys. 22 May 2000; 112 (20): 8910–8922. https://doi.org/10.1063/1.481505
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