Spectroscopically determined potential energy surfaces of the H2O, H2O, and H2O isotopologues of water |
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Authors: | Sergei V Shirin Oleg L Polyansky Nikolai F Zobov Roman I Ovsyannikov Jonathan Tennyson |
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Institution: | a Department of Physics and Astronomy, University College London, London WC1E 6BT, UK b Sektion Spektren und Strukturdokumentation, University of Ulm, D-89069, Ulm, Germany c Institute of Chemistry, Eötvös University, P.O. Box 32, H-1518 Budapest 112, Hungary d Institute of Applied Physics, Russian Academy of Science, Uljanov Street 46, Nizhnii Novgorod 603950, Russia |
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Abstract: | Adiabatic potential energy surfaces (PESs) for three major isotopologues of water, H216O, H217O, and H218O, are constructed by fitting to observed vibration-rotation energy levels of the system using the nuclear motion program DVR3D employing an exact kinetic energy operator. Extensive tests show that the mass-dependent ab initio surfaces due to Polyansky et al. O.L. Polyansky, A.G. Császár, S.V. Shirin, N.F. Zobov, P. Barletta, J. Tennyson, D.W. Schwenke, P.J. Knowles, Science 299 (2003) 539-542.] provide an excellent starting point for the fits. The refinements are performed using a mass-independent morphing function, which smoothly distorts the original adiabatic ab initio PESs. The best overall fit is based on 1788 experimental energy levels with the rotational quantum number J = 0, 2, and 5. It reproduces these levels with a standard deviation of 0.079 cm−1 and gives, when explicit allowance is made for nonadiabatic rotational effects, excellent predictions for levels up to J = 40. Theoretical linelists for all three isotopologues of water involved in the PES construction were calculated up to 26 000 cm−1 with energy levels up to J = 10. These linelists should make an excellent starting point for spectroscopic modelling and analysis. |
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Keywords: | Water vapour Line assignments Atmospheric radiation Adiabatic potential energy surface Rotational nonadiabaticity |
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