A multispectrum analysis of the ν2 band of H12C14N: Part II. Theoretical calculations of self-broadening, self-induced shifts, and their temperature dependences

A semiclassical theory based upon the Robert–Bonamy formalism has been developed to explain the experimental measurements of self-broadening, self-induced pressure shift coefficients in the m1,m2 ,2 m2 bands of H 12 C 14 N and the 2m1 band of H 13 C 14 N, as well as the temperature dependences of these parameters with special emphasis on the m2 band. Our calculations include only electrostatic interactions and neglect the vibrational dependence of the isotropic part of the intermolecular potential, which probably has a weak contribution to the HCN self-shifts for the bands investigated in this study. The agreement between theory and measurements is good in the cases of self-broadening coefficients and their variation with temperature, as well as the self-shift coefficients determined at room temperature. However, the observed temperature dependence of self-shift coefficients in the m2 band is different from that derived theoretically.

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