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

Attila G. Császár, J. Sophie Kain, Oleg L. Polyansky, Nikolai F. Zobov, Jonathan Tennyson

Research output: Contribution to journalArticle

51 Citations (Scopus)

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 H216O. These calculations suggest that the relativistic correction, has a stronger influence on 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 Ka.

Original languageEnglish
Pages (from-to)317-323
Number of pages7
JournalChemical Physics Letters
Volume293
Issue number3-4
DOIs
Publication statusPublished - Aug 28 1998

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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