Vibration–rotation variational calculations: Precise results on HCN up to 25 000 cm-1

Carter, Stuart; Mills, Ian M.; Handy, Nicholas C.
September 1993
Journal of Chemical Physics;9/15/1993, Vol. 99 Issue 6, p4379
Academic Journal
Variation calculations of the vibration–rotation energy levels of many isotopomers of HCN are reported, for J=0, 1, and 2, extending up to approximately 8 quanta of each of the stretching vibrations and 14 quanta of the bending mode. The force field, which is represented as a polynomial expansion in Morse coordinates for the bond stretches and even powers of the angle bend, has been refined by least squares to fit simultaneously all observed data on the Σ and Π state vibrational energies, and the Σ state rotational constants, for both HCN and DCN. The observed vibrational energies are fitted to roughly ±0.5 cm-1, and the rotational constants to roughly ±0.0001 cm-1. The force field has been used to predict the vibration rotation spectra of many isotopomers of HCN up to 25 000 cm-1. The results are consistent with the axis-switching assignments of some weak overtone bands reported recently by Jonas, Yang, and Wodtke, and they also fit and provide the assignment for recent observations by Romanini and Lehmann of very weak absorption bands above 20 000 cm-1.


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