l-resonance perturbations in infrared perpendicular bands
Cartwright, G. J. and Mills, I. (1970) l-resonance perturbations in infrared perpendicular bands. Journal of Molecular Spectroscopy, 34 (3). pp. 415-439. ISSN 0022-2852
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To link to this article DOI: 10.1016/0022-2852(70)90024-X
The effects of ℓ-type resonance on rovibrational bands in infrared spectra are reviewed. Observed spectra are compared with computer-simulated spectra obtained by solving the Hamiltonian matrix numerically and calculating the true (perturbed) wavenumber and intensity of each line in the band. The most obvious effects in the spectra are shown to result from intensity perturbations rather than line-shifts; in oblate symmetric tops the Q branch structure near the band center may show anomalies due to ℓ-resonance even at quite low resolution and even when the accidental resonance is not very exact. Numerical values of ℓ-doubling constants are obtained for several cyclopropane bands by comparing observed band contours at about 0.2-cm−1 resolution with computed contours. Although the constants are not determined with great precision, the sign of the ℓ-doubling constants is determined unambiguously.
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