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A new ab initio ground-state dipole moment surface for the water molecule

By L Lodi, RN Tolchenov, J Tennyson, AE Lynas-Gray, SV Shirin, NF Zobov, OL Polyansky, AG Csaszar, JNP van Stralen and L Visscher

Abstract

A valence-only (V) dipole moment surface (DMS) has been computed for water at the internally contracted multireference configuration interaction level using the extended atom-centered correlation-consistent Gaussian basis set aug-cc-pV6Z. Small corrections to these dipole values, resulting from core correlation (C) and relativistic (R) effects, have also been computed and added to the V surface. The resulting DMS surface is hence called CVR. Interestingly, the C and R corrections cancel out each other almost completely over the whole grid of points investigated. The ground-state CVR dipole of (H2O)-O-16 is 1.8676 D. This value compares well with the best ab initio one determined in this study, 1.8539 +/- 0.0013 D, which in turn agrees well with the measured ground-state dipole moment of water, 1.8546(6) D. Line intensities computed with the help of the CVR DMS shows that the present DMS is highly similar to though slightly more accurate than the best previous DMS of water determined by Schwenke and Partridge [J. Chem. Phys. 113, 16 (2000)]. The influence of the precision of the rovibrational wave functions computed using different potential energy surfaces (PESs) has been investigated and proved to be small, due mostly to the small discrepancies between the best ab initio and empirical PESs of water. Several different measures to test the DMS of water are advanced. The seemingly most sensitive measure is the comparison between the ab initio line intensities and those measured by ultralong pathlength methods which are sensitive to very weak transitions. (c) 2008 American Institute of Physics

Topics: POTENTIAL-ENERGY SURFACE, VIBRATION-ROTATION LEVELS, BORN-OPPENHEIMER APPROXIMATION, HELLMANN-FEYNMAN THEOREM, GAUSSIAN-BASIS SETS, 1ST-ORDER PROPERTIES, WAVE-FUNCTIONS, RELATIVISTIC CORRECTIONS, ELECTRIC PROPERTIES, EXPECTATION VALUE
Publisher: AMER INST PHYSICS
Year: 2008
OAI identifier: oai:eprints.ucl.ac.uk.OAI2:17027
Provided by: UCL Discovery
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