Journal
JOURNAL OF QUANTITATIVE SPECTROSCOPY & RADIATIVE TRANSFER
Volume 111, Issue 9, Pages 1043-1064Publisher
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.jqsrt.2010.02.009
Keywords
Water vapor; Transition wavenumbers; Atmospheric physics; Energy levels; Assignation
Categories
Funding
- Scientific Research Fund of Hungary [K72885]
- European Union
- UK NERC
- Russian Fund for Basic Research
- EPSRC [EP/E043674/1] Funding Source: UKRI
- NERC [NE/F01967X/1] Funding Source: UKRI
- STFC [ST/H008543/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/E043674/1] Funding Source: researchfish
- Natural Environment Research Council [NE/F01967X/1] Funding Source: researchfish
- Science and Technology Facilities Council [ST/H008543/1] Funding Source: researchfish
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A new, accurate, global, mass-independent, first-principles potential energy surface (PES) is presented for the ground electronic state of the water molecule. The PES is based on 2200 energy points computed at the all-electron aug-cc-pCV6Z IC-MRCI(8,2) level of electronic structure theory and includes the relativistic one-electron mass-velocity and Darwin corrections. For H-2 O-16, the PES has a dissociation energy of D-0 = 41 109 cm(-1) and supports 1150 vibrational energy levels up to 41 083 cm(-1). The deviation between the computed and the experimentally measured energy levels is below 15 cm(-1) for all the states with energies less than 39000 cm(-1). Characterization of approximate vibrational quantum numbers is performed using several techniques: energy decomposition, wave function plots, normal mode distribution, expectation values of the squares of internal coordinates, and perturbing the bending part of the PES. Vibrational normal mode labels, though often not physically meaningful, have been assigned to all the states below 26 500 cm(-1) and to many more above it, including some highly excited stretching states all the way to dissociation. Issues to do with calculating vibrational band intensities for the higher-lying states are discussed. (C) 2010 Elsevier Ltd. All rights reserved.
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