Comparison of experiment and theory for the resonance Raman spectrum of I2 in solution. II. The Raman excitation and depolarization profiles in n-hexane

Abstract

The calculations for I2 in n-hexane, which were started in paper I [J. Chem. Phys. 85, 3791 (1986)] are improved by considering the effect of the D state and of charge–tranfer states. Changes in intensities and positions of the B states and the effect of the rotation of I2 in 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 profile—a discrepancy for which we have not found an explanation. The depolarization ratios of the overtones may be explained by shifting the B and B″ states about 200 cm−1 further 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.