The parametrization of a Thole-type all-atom polarizable water model from first principles and its application to the study of water clusters ({bold {ital n}}=2{endash}21) and the phonon spectrum of ice Ih

Journal Article · Mon Mar 01 04:00:00 EST 1999 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.478797· OSTI ID:321483

Burnham, C J; Li, J ^[1]; Xantheas, S S ^[2]; Leslie, M ^[3]

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1. Department of Physics, UMIST, P.O. Box 88, Manchester, M60 1QD (United Kingdom)
2. Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 906 Battelle Boulevard, MS K1-96, Richland, Washington 99352 (United States)
3. Daresbury Laboratory, CCLRC, Warrington, WA4 4AD (United Kingdom)

We present the parametrization of a new polarizable model for water based on Thole{close_quote}s method [{ital Chem. Phys.} {bold 59}, 341 (1981)] for predicting molecular polarizabilities using smeared charges and dipoles. The potential is parametrized using first principles {ital ab initio} data for the water dimer. Initial benchmarks of the new model include the investigation of the properties of water clusters (n=2{endash}21) and (hexagonal) ice Ih using molecular dynamics simulations. The potential produces energies and nearest-neighbor (H-bonded) oxygen{endash}oxygen distances that agree well with the {ital ab initio} results for the small water clusters. The properties of larger clusters with 9{endash}21 water molecules using predicted structures from Wales {ital et al.} [Chem. Phys. Lett. {bold 286}, 65 (1998)] were also studied in order to identify trends and convergence of structural and electric properties with cluster size. The simulation of ice Ih produces a lattice energy of {minus}65.19 kJ/mol (expt. {minus}58.9 kJ/mol) with an average dipole moment of 2.849 D. The calculated spectrum for the phonon density of states exhibits features that may correspond to the experimentally measured peaks at 28 and 37 meV. The many body contribution to the total energy is found to be close to 31{percent} for both the water clusters and for ice Ih. {copyright} {ital 1999 American Institute of Physics.}

• OSTI ID: 321483
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 9 Vol. 110; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

66 PHYSICS
CRYSTAL STRUCTURE
ICE
LIQUIDS
MOLECULAR CLUSTERS
MOLECULAR DYNAMICS METHOD
PHONONS
POLARIZABILITY
STRUCTURE FUNCTIONS
VIBRATIONAL STATES
WATER