Accurate ab initio potential energy curve of F2. III. The vibration rotation spectrum

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2007-11-30
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Gordon, Mark
Matsunaga, N.
Nagata, T.
Gordon, Mark S.
Ruedenberg, K.
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American Institute of Physics
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Chemistry
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Ames Laboratory
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ChemistryAmes Laboratory
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 F2 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 5cm−1 over the 22 levels. The dissociation energy with respect to the lowest vibrational energy is calculated within 30cm−1 of the experimental value of 12953±8cm−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.
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This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in Bytautas, Laimutis, Nikita Matsunaga, Takeshi Nagata, Mark S. Gordon, and Klaus Ruedenberg. "Accurate ab initio potential energy curve of F 2. III. The vibration rotation spectrum." The Journal of Chemical Physics 127, no. 20 (2007): 204313, and may be found at DOI: 10.1063/1.2805392. Copyright 2007 American Institute of Physics. Posted with permission.
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