Microstructure of ambient and supercritical water. Direct comparison between simulation and neutron scattering experiments
- Univ. of Tennessee, Knoxville, TN (United States)
Molecular dynamics simulations of SPC, SPC/E, TIP4P, and ST2 water models are performed at ambient and two supercritical conditions make a direct comparison with recent microstructural data obtained by neutron diffraction with isotopic substitution (NDIS) experiments. The models generally fail to accurately predict details of the NDIS results at supercritical conditions, even though they are somewhat successful at ambient conditions. The failure is not as pronounced as that expected by Postorino et al. because of an unusual density dependence in the structure predicted by two of the models. We also evaluate a model for supercritical water denoted SPCG, a modification of the SPC and SPC/E models, in which the dipole moment is reduced to the bare dipole moment of water. For this model, the predicted structure at supercritical conditions is in much better agreement with experiment. A geometric definition of hydrogen bonding is used to gain insight into the angular dependence of the H...O pair distribution function g{sub OH}(r,{omega}). The simulation results for the five models indicate a strong orientational dependence for the g{sub OH}(r,{omega}) along the H-bonding orientations, with an approximately constant relative strength from ambient to supercritical conditions, suggesting that the angle-averaged radial distribution function, g{sub OH}(r), and its volume integral over the first solvation shell, n{sub OH}(r), may not in themselves be good measures of the strength of the H-bonding. 46 refs., 15 figs., 2 tabs.
- OSTI ID:
- 200395
- Journal Information:
- Journal of Physical Chemistry, Vol. 100, Issue 4; Other Information: PBD: 25 Jan 1996
- Country of Publication:
- United States
- Language:
- English
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