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Title: Geometry-dependent distributed polarizability models for the water molecule

Geometry-dependent distributed polarizability models have been constructed by fits to ab initio calculations at the coupled cluster level of theory with up to noniterative triple excitations in an augmented triple-zeta quality basis set for the water molecule in the field of a point charge. The investigated models include (i) charge-flow polarizabilities between chemically bonded atoms, (ii) isotropic or anisotropic dipolar polarizabilities on oxygen atom or on all atoms, and (iii) combinations of models (i) and (ii). For each model, the polarizability parameters have been optimized to reproduce the induction energy of a water molecule polarized by a point charge successively occupying a grid of points surrounding the molecule. The quality of the models is ascertained by examining their ability to reproduce these induction energies as well as the molecular dipolar and quadrupolar polarizabilities. The geometry dependence of the distributed polarizability models has been explored by changing bond lengths and HOH angle to generate 125 molecular structures (reduced to 75 symmetry-unique ones). For each considered model, the distributed polarizability components have been fitted as a function of the geometry by a Taylor expansion in monomer coordinate displacements up to the sum of powers equal to 4.
Authors:
; ; ;  [1] ;  [2] ;  [3]
  1. Université de Lorraine, SRSMC UMR 7565, Vandoeuvre-les-Nancy F-54506 (France)
  2. (France)
  3. Department of Physics and Astronomy, University of Delaware, Newark, Delaware 19716 (United States)
Publication Date:
OSTI Identifier:
22493665
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 144; Journal Issue: 3; Other Information: (c) 2016 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANISOTROPY; ATOMS; BOND LENGTHS; CHEMICAL BONDS; EXCITATION; HYDROGEN; INDUCTION; MOLECULAR STRUCTURE; MOLECULES; MONOMERS; OXYGEN; POINT CHARGE; POLARIZABILITY; WATER