Infrared and microwave study of angular–radial coupling effects in Ar–HCN

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Abstract
Microwave and infrared spectra of Ar–HCN have been obtained using an electric-resonance optothermal spectrometer. The microwave measurements extend to higher J the previous results of Leopold et al. and Klots et al., allowing the determination of higher-order centrifugal distortion constants for this quasilinear, highly nonrigid complex. A Padé approximant fit to the microwave data indicates a significant rotation-induced asymptotic increase in the zero-point center-of-mass separation between the Ar and the HCN, above that expected from pure radial distortion. This results from the large coupling between the angular and radial degrees in the intermolecular potential forcing the centrifugal alignment of the HCN. Infrared spectra are reported for the C–H streching fundamental ν1 and the combination band ν1+ν15, where ν5 is the van der Waals bending vibration. The band-origin difference between these two bands gives ν5=7.8 cm−1, in rough agreement with the 10 cm−1 harmonic value predicted from the microwave-determined nuclear quadrupole coupling constant. The complexation-induced red shift of the C–H stretching vibration is 2.69 cm−1 and the vibrational predissociation linewidths Γ are <10 MHz (FWHM). The vibrationally excited complex predissociates before striking the bolometer detector, implying that the predissociation lifetime τ<1 ms.