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Simultaneous Rovibrational Analysis of the ν2, ν3, ν5, and ν6 Bands of H312CF

✍ Scribed by D. Papoušek; P. Pracna; M. Winnewisser; S. Klee; J. Demaison

Publisher
Elsevier Science
Year
1999
Tongue
English
Weight
107 KB
Volume
196
Category
Article
ISSN
0022-2852

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✦ Synopsis

A total of 4892 transition wavenumbers of the 2 , 3 , 5 , and 6 fundamental bands of H 3 12 CF and 1469 frequencies of the rotational transitions in the v 2 ϭ 1, v 3 ϭ 1, v 5 ϭ 1, and v 6 ϭ 1 vibrational states have been fitted simultaneously by taking explicitly into account various Coriolis interactions, l-type interactions, and ␣-resonance terms between and within the vibrational states. The standard deviation of the fit using 71 parameters was 8.10 ϫ 10 Ϫ5 cm Ϫ1 for the infrared data and 0.198 MHz for the rotational data. This study clearly shows that in order to obtain a really quantitative fit of the highly precise data of vibration-rotational and rotational spectroscopy, it is necessary to fit all the data simultaneously using a variational approach. The deperturbed values of the upper state rotational constants differ significantly from those obtained previously in fitting the 3 and 6 bands as isolated bands and the 2 / 5 bands by a variational approach. This is important for the precise determination of the equilibrium structure of methyl fluoride (J. Demaison, J. Breidung, W. Thiel, and D. Papous ˇek, Struct. Chem., in press). Besides this, the results can be used in further studies of the reduced Hamiltonians for more complicated systems of interacting vibrational levels.

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