Sub-Doppler resolution infrared spectra of the isoelectronic pair: N2–HCN and OC–HCN

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Abstract
Sub‐Doppler resolution infrared spectra have been obtained for the ν1 bands of N2 –HCN and OC–HCN using the opto‐thermal detection method, from which accurate ground and excited state molecular constants are determined. Vibrational predissociation lifetimes are estimated from the homogeneous broadening of the observed transitions, giving lifetimes of 80 and 2.6 ns for N2 –HCN and OC–HCN, respectively. These lifetimes are considerably longer than those obtained previously for N2 –HF and OC–HF. This difference can be understood in terms of the strength of the coupling between the intra‐ and intermolecular motions, which is also reflected in the vibrational frequency shift associated with complex formation.