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Calculating energy levels of isomerizing tetra-atomic molecules. II. The vibrational states of acetylene and vinylidene

Kozin, I.N.; Law, M.M.; Tennyson, J.; Hutson, J.M.

Calculating energy levels of isomerizing tetra-atomic molecules. II. The vibrational states of acetylene and vinylidene Thumbnail


Authors

I.N. Kozin

M.M. Law

J. Tennyson



Abstract

A general, full-dimensional computational method for the accurate calculation of rotationally and vibrationally excited states of tetra-atomic molecules is further developed. The resulting computer program may be run in serial and parallel modes and is particularly appropriate for molecules executing wide-amplitude motions and isomerizations. An application to the isomerizing acetylene∕vinylidene system is presented. Large-scale calculations using a coordinate system based on orthogonal satellite vectors have been performed in six dimensions and vibrational term values and wave functions for acetylene and vinylidene states up to ≈23000cm−1 above the potential minimum have been determined. This has permitted the characterization of acetylene and vinylidene states at and above the isomerization barrier. These calculations employ more extensive vibrational basis sets and hence consider a much higher density of states than in any variational calculations reported hitherto for this system. Comparison of the calculated density of states with that determined empirically suggests that our calculations are the most realistic achieved for this system to date. Indeed more states have been converged than in any previous study of this system. Calculations on lower lying excited states of acetylene based on HC–CH diatom-diatom coordinates give nearly identical results to those based on orthogonal satellite vectors. Comparisons are also made with calculations based on HH–CC diatom-diatom coordinates.

Citation

Kozin, I., Law, M., Tennyson, J., & Hutson, J. (2005). Calculating energy levels of isomerizing tetra-atomic molecules. II. The vibrational states of acetylene and vinylidene. The Journal of Chemical Physics, 122(6), https://doi.org/10.1063/1.1850471

Journal Article Type Article
Acceptance Date Nov 30, 2004
Publication Date Feb 8, 2005
Deposit Date Aug 19, 2015
Publicly Available Date Mar 28, 2024
Journal Journal of Chemical Physics
Print ISSN 0021-9606
Electronic ISSN 1089-7690
Publisher American Institute of Physics
Peer Reviewed Peer Reviewed
Volume 122
Issue 6
DOI https://doi.org/10.1063/1.1850471

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Copyright Statement
© 2005 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in The Journal of Chemical Physics 122, 064309 (2005) and may be found at http://dx.doi.org/10.1063/1.1850471




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