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Relativistic correction to the potential energy surface and vibration-rotation levels of water

Authors :
Jonathan Tennyson
J.Sophie Kain
Nikolai F. Zobov
Attila G. Császár
Oleg L. Polyansky
Source :
Chemical Physics Letters. 293:317-323
Publication Year :
1998
Publisher :
Elsevier BV, 1998.

Abstract

The relativistic correction to the electronic energy of the water molecule is calculated as a function of geometry using . CCSD T wavefunctions and first-order perturbation theory applied to the one-electron mass-velocity and Darwin terms. Based on the calculated 324 energy points, a fitted relativistic correction surface is constructed. This surface is used with a high-accuracy ab initio non-relativistic Born-Oppenheimer potential energy surface to calculate the vibrational band origins and rotational term values for H 16 O. These calculations suggest that the relativistic correction, has a stronger influence on 2 the vibration-rotation levels of water than the Born-Oppenheimer diagonal correction. The effect is particularly marked for vibrational levels with bending excitation or rotational states with high K. q 1998 Elsevier Science B.V. All rights a reserved.

Details

ISSN :
00092614
Volume :
293
Database :
OpenAIRE
Journal :
Chemical Physics Letters
Accession number :
edsair.doi...........cb31b68acf7ce96393b4595ff313dd7c
Full Text :
https://doi.org/10.1016/s0009-2614(98)00697-6