The anharmonic stretching-bending potential of CO2 from inversion of spectroscopic data

H. Romanowski, R. B. Gerber, Mark A Ratner

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Abstract

The full anharmonic stretching and bending potential of CO2 is determined to high accuracy from the measured vibration/rotation spectrum. The calculation consists of two stages: first, a direct explicit inversion of the data within a semiclassical self-consistent-field (SCF) treatment of vibrational dynamics and second, a refinement of this result by a first-order perturbative approach that includes corrections to the SCF approximation, but assumes that the SCF-inverted potential shows only small deviations from the true surface. The final result is tested by comparison of the energy levels calculated exactly from the determined potential against the original experimental input. Based on this criterion of accuracy in reproducing experimental frequencies, the present inverted potential appears more accurate than previous potentials obtained from empirical fitting of the data. These results indicate that the perturbatively corrected SCF inversion method is a very powerful tool for obtaining potential energy surfaces directly from experimental data, with errors not exceeding several wave numbers.

Original languageEnglish
Pages (from-to)6757-6767
Number of pages11
JournalJournal of Chemical Physics
Volume88
Issue number11
Publication statusPublished - 1988

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ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

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