Transferable Potential Function for Flexible H2O Molecules Based on the Single-Center Multipole Expansion

Journal of Chemical Theory and Computation, vol. 18, pp. 7528–7543

Abstract

A potential function is presented for describing a system of flexible H 2 O molecules based on the single-center multipole expansion (SCME) of the electrostatic interaction. The model, referred to as SCME/f, includes the variation of the molecular quadrupole moment as well as the dipole moment with changes in bond length and angle so as to reproduce results of high-level electronic structure calculations. The multipole expansion also includes fixed octupole and hexadecapole moments, as well as anisotropic dipole–dipole, dipole–quadrupole, and quadrupole–quadrupole polarizability tensors. The model contains five adjustable parameters related to the repulsive interaction and damping functions in the electrostatic and dispersion interactions. Their values are adjusted to reproduce the lowest energy isomers of small clusters, (H 2 O) n with n = 2–6, as well as measured properties of the ice Ih crystal. Subsequent calculations of the energy difference between the various isomer configurations of the clusters show that SCME/f gives good agreement with results of electronic structure calculations and represents a significant improvement over the previously presented rigid SCME potential function. Analysis of the vibrational frequencies of the clusters and structural properties of ice Ih crystal show the importance of accurately describing the variation of the quadrupole moment with molecular structures.

Authors 5

1. Elvar Ö. Jónsson corresponding

   University of Iceland

   Affiliation as printed

   Science Institute and Faculty of Physical Sciences, University of Iceland, VR-III, 107Reykjavík, Iceland

2. Soroush Rasti Aachen Leiden Institute of Chemistry, Gorlaeus Laboratories

   Leiden University

   Affiliation as printed

   Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, 2300 RALeiden, The Netherlands

3. Marta Gałyńska

   University of Iceland

   Affiliation as printed

   Science Institute and Faculty of Physical Sciences, University of Iceland, VR-III, 107Reykjavík, Iceland

4. Jörg Meyer Aachen Leiden Institute of Chemistry, Gorlaeus Laboratories

   Leiden University

   Affiliation as printed

   Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, 2300 RALeiden, The Netherlands

5. Hannes Jónsson

   University of Iceland

   Affiliation as printed

   Science Institute and Faculty of Physical Sciences, University of Iceland, VR-III, 107Reykjavík, Iceland