Accurate ab initio potential energy curve of F-2. III. The vibration rotation spectrum

TitleAccurate ab initio potential energy curve of F-2. III. The vibration rotation spectrum
Publication TypeJournal Article
Year of Publication2007
AuthorsBytautas L, Matsunaga N, Nagata T, Gordon MS, Ruedenberg K
Journal TitleJournal of Chemical Physics
Volume127
Pages204313
Date PublishedNov
Type of ArticleReview
ISBN Number0021-9606
Accession NumberISI:000251325100022
KeywordsATOMIC ORBITALS, CONFIGURATION-INTERACTION CALCULATIONS, DISCRETE VARIABLE REPRESENTATION, ELECTRONIC SCHRODINGER-EQUATION, EQUILIBRIUM BOND DISTANCES, molecular wave-functions, MULTIREFERENCE COUPLED-CLUSTER, self-consistent-field, TEMPERED, TRANSITION-S
Abstract

An analytical expression is found for the accurate ab initio potential energy curve of the fluorine molecule that has been determined in the preceding two papers. With it, the vibrational and rotational energy levels of F-2 are calculated using the discrete variable representation. The comparison of this theoretical spectrum with the experimental spectrum, which had been measured earlier using high-resolution electronic spectroscopy, yields a mean absolute deviation of about 5 cm(-1) over the 22 levels. The dissociation energy with respect to the lowest vibrational energy is calculated within 30 cm(-1) of the experimental value of 12 953 +/- 8 cm(-1). The reported agreement of the theoretical spectrum and dissociation energy with experiment is contingent upon the inclusion of the effects of core-generated electron correlation, spin-orbit coupling, and scalar relativity. The Dunham analysis [Phys. Rev. 41, 721 (1932)] of the spectrum is found to be very accurate. New values are given for the spectroscopic constants. (c) 2007 American Institute of Physics.

DOI10.1063/1.2805392
Alternate JournalJ. Chem. Phys.