Comparison of simple potential functions for simulating liquid water

Jorgensen, William L.; Chandrasekhar, Jayaraman; Madura, Jeffry D.; Impey, Roger W.; Klein, Michael L.

doi:doi:10.1063/1.445869

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A molecular dynamics simulation of rotational and vibrational relaxation in liquid HCl

We have carried out a molecular dynamics simulation of liquid HCl near its normal boiling point using the C∗ potential of Klein and McDonald. A wide variety of equilibrium and dynamical properties have been studied, ranging from partial structure factors to velocity, angular velocity, and torque autocorrelation functions. Dipole moment and polarizability tensor correlation functions have been evaulated and compared with experimental data from dielectric relaxation and Raman line shape studies. V...

Density fluctuation in a ‘‘Theorist’s ideal glass’’

The density fluctuation in glassy materials can be considered to consist of dynamic and quasistatic contributions, the dynamic part being related to the compressibility of the glass determined on the same experimental time scale as the measurement of the density fluctuation. A justification for such an assumption, and a clarification of the meanings of the terms dynamic and quasistatic density fluctuation are obtained through the concept of ‘‘theorist’s ideal glass’’ which was originally describ...

Classical Monte Carlo simulations have been carried out for liquid water in the NPT ensemble at 25 °C and 1 atm using six of the simpler intermolecular potential functions for the water dimer: Bernal–Fowler (BF), SPC, ST2, TIPS2, TIP3P, and TIP4P. Comparisons are made with experimental thermodynamic and structural data including the recent neutron diffraction results of Thiessen and Narten. The computed densities and potential energies are in reasonable accord with experiment except for the original BF model, which yields an 18% overestimate of the density and poor structural results. The TIPS2 and TIP4P potentials yield oxygen–oxygen partial structure functions in good agreement with the neutron diffraction results. The accord with the experimental OH and HH partial structure functions is poorer; however, the computed results for these functions are similar for all the potential functions. Consequently, the discrepancy may be due to the correction terms needed in processing the neutron data or to an effect uniformly neglected in the computations. Comparisons are also made for self‐diffusion coefficients obtained from molecular dynamics simulations. Overall, the SPC, ST2, TIPS2, and TIP4P models give reasonable structural and thermodynamic descriptions of liquid water and they should be useful in simulations of aqueous solutions. The simplicity of the SPC, TIPS2, and TIP4P functions is also attractive from a computational standpoint.

KEYWORDS and PACS

Keywords

water, computerized simulation, monte carlo method, intermolecular forces, potentials, structure factors, liquids, medium temperature, self−diffusion, hydrogen bonds

PACS

61.20.Ja

Computer simulation of liquid structure
61.20.Qg

Structure of associated liquids: electrolytes, molten salts, etc.
34.20.-b

Interatomic and intermolecular potentials and forces, potential energy surfaces for collisions
66.10.C-

Diffusion and thermal diffusion