The infrared spectroscopy and dynamics of OCO–HCl and SCO–HCl: An example of mode specific intermolecular energy transfer

Oudejans, L.; Olson, D.; Miller, R. E.
November 1996
Journal of Chemical Physics;11/15/1996, Vol. 105 Issue 19, p8515
Academic Journal
Optothermal near infrared laser spectroscopy has been used to study the OCO–HCl and SCO–HCl complexes by exciting the H–Cl stretch using an F-center laser. In both cases, the two isotopic forms associated with H35Cl and H37Cl have been observed. All of the observed spectra are consistent with and analyzed in terms of a linear structure. Vibrational predissociation is observed to be abnormally fast in the OCO–HCl complex, considering the rather weak coupling between the intermolecular degrees of freedom and the H–Cl stretch suggested by the small vibrational frequency shift associated with complex formation. Comparisons are made between the two systems studied here that indicate that this anomalous rate is due to a near resonance between the energy available to the fragments after the photodissociation of the complex and the asymmetric stretch of the CO2 fragment. © 1996 American Institute of Physics.


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