Time-dependent analysis of the Hartley absorption band and resonance Raman spectra in ozone

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Abstract
A detailed investigation is made of the short‐time dynamics involved in the Hartley absorption band in ozone and the related resonance Raman spectra for low vibrational overtones. A quadratic expansion of the X 1A1 and dissociative 1B2 potential energy surfaces involved leads to an analytic calculation of three‐mode vibrational correlation functions, which are then Fourier‐transformed to obtain the absorption and Raman spectra. A type of time‐dependent perturbation theory is used to approximate the effects of including anharmonic terms in the expansion of the upper state. It is concluded that an improvement in the description of the Raman spectra will require at the least a major modification of the parabolic barrier behavior along the antisymmetric stretch coordinate and, better, a large‐amplitude‐motion treatment.