Infrared shifts of the water dimer from the fully flexible ab initio HBB2 potential
We report calculations of the infrared shifts for the water dimer, as obtained from the recent ab initio fully flexible HBB2 potential of Bowman and co-workers. The rovibrational calculations, which formally are 12-dimensional plus overall rotation, were performed within the [6+6]d adiabatic separat...
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Published in | Philosophical transactions of the Royal Society of London. Series A: Mathematical, physical, and engineering sciences Vol. 370; no. 1968; pp. 2675 - 2690 |
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Main Author | |
Format | Journal Article |
Language | English |
Published |
England
The Royal Society Publishing
13.06.2012
The Royal Society |
Subjects | |
Online Access | Get full text |
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Summary: | We report calculations of the infrared shifts for the water dimer, as obtained from the recent ab initio fully flexible HBB2 potential of Bowman and co-workers. The rovibrational calculations, which formally are 12-dimensional plus overall rotation, were performed within the [6+6]d adiabatic separation which decouples the 'fast' intramolecular modes from the 'slow' intermolecular ones. Apart from this decoupling, each set of modes is treated in a fully variational approach. The intramolecular motion was described in terms of Radau coordinates, using the f-embedding formulation of Wei & Carrington, and neglecting the rovibrational Coriolis coupling terms. Within this adiabatic approximation, the intermolecular motion is handled in a similar way as for rigid monomers, except for the rotational constants B's, averaged over intramolecular modes that depend now on the intermolecular geometry. Comparison with experimental data shows an excellent overall agreement. |
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Bibliography: | href:rsta20110187.pdf ArticleID:rsta20110187 One contribution of 17 to a Theo Murphy Meeting Issue 'Water in the gas phase'. istex:E44DB237BC66BCCE341AB1B986CF54B12411ECF7 ark:/67375/V84-G5S0HZ61-3 Theo Murphy Meeting Issue 'Water in the gas phase' compiled and edited by Jonathan Tennyson and Keith P. Shine ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 1364-503X 1471-2962 |
DOI: | 10.1098/rsta.2011.0187 |