Comparison of experiment and theory for the resonance Raman spectrum of I2in solution. II. The Raman excitation and depolarization profiles innhyphen;hexane

摘要

The calculations for I2innhyphen;hexane, which were started in paper I lsqb;J. Chem. Phys.85, 3791 (1986)rsqb; are improved by considering the effect of theDstate and of chargendash;tranfer states. Changes in intensities and positions of theBstates and the effect of the rotation of I2in the excited states are also considered. The experimental excitation profiles are recalibrated and compared to calculations. The depolarization profiles are measured and are also compared to calculations. The measured Raman cross sections are higher than calculated in the high frequency wing of the profilemdash;a discrepancy for which we have not found an explanation. The depolarization ratios of the overtones may be explained by shifting theBandBlsquo;states about 200 cmminus;1further apart than in the gas phase and by taking into account the effect of rotation of the I2. The excited state relaxation time,T2, is still determined as about 0.3 ps.