Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
5416060 | Journal of Molecular Spectroscopy | 2006 | 8 Pages |
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 JÂ =Â 0, 2, and 5. It reproduces these levels with a standard deviation of 0.079Â cmâ1 and gives, when explicit allowance is made for nonadiabatic rotational effects, excellent predictions for levels up to JÂ =Â 40. Theoretical linelists for all three isotopologues of water involved in the PES construction were calculated up to 26Â 000Â cmâ1 with energy levels up to JÂ =Â 10. These linelists should make an excellent starting point for spectroscopic modelling and analysis.
Related Topics
Physical Sciences and Engineering
Chemistry
Physical and Theoretical Chemistry
Authors
Sergei V. Shirin, Oleg L. Polyansky, Nikolai F. Zobov, Roman I. Ovsyannikov, Attila G. Császár, Jonathan Tennyson,