Abstract
A method for estimating vibrational quantum numbers of vibrationally excited transients in solution is proposed. In this method, we calculate anti-Stokes Raman excitation profiles (REPs) which are characteristic of the initial vibrational states involved in the Raman process, and compare them with observed anti-Stokes intensities. We have applied this method to vibrationally hot molecules of canthaxanthin in the So state and those of trans-stilbene in the S1 state. For canthaxanthin, it has been found that the vibrationally excited transients are for the most part on the ν=1 level of the C═C stretching mode, and that excess vibrational energy is statistically distributed among all intramolecular vibrational modes. As for S1 stilbene, vibrational transients are shown to be mostly on the ν=1 level for two vibrational modes examined, while the excess vibrational energy is probably localised on the olefinic C═C stretching mode.
Highlights
In recent ultrafast studies in solution, knowledge on the intramolecular vibrational redistribution (IVR) processes is increasing
It is important to specify the vibrational quantum states of observed vibrationally excited transients in order to clarify the mechanism of vibrational relaxation
The present result suggests that vibrational energy localised first on the C--C stretch is very rapidly redistributed among all vibrational modes
Summary
A method for estimating vibrational quantum numbers of vibrationally excited transients in solution is proposed In this method, we calculate anti-Stokes Raman excitation profiles (REPs) which are characteristic of the initial vibrational states involved in the Raman process, and compare them with observed anti-Stokes intensities. We calculate anti-Stokes Raman excitation profiles (REPs) which are characteristic of the initial vibrational states involved in the Raman process, and compare them with observed anti-Stokes intensities We have applied this method to vibrationally hot molecules of canthaxanthin in the So state and those of trans-stilbene in the S1 state. It has been found that the vibrationally excited transients are for the most part on the v level of the C =C stretching mode, and that excess vibrational energy is statistically distributed among all intramolecular vibrational modes.
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