Excited-state structure and electronic dephasing time of Nile blue from absolute resonance Raman intensities

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Abstract
Absolute resonance Raman cross sections are measured for Nile blue 690 perchlorate dissolved in ethylene glycol with excitation at 514, 531, and 568 nm. These values and the absorptionspectrum are modeled using a time‐dependent wave packet formalism. The excited‐state equilibrium geometry changes are quantitated for 40 resonance Raman active modes, seven of which (590, 1141, 1351, 1429, 1492, 1544, and 1640 cm−1 ) carry 70% of the total resonance Raman intensity. This demonstrates that in addition to the prominent 590 and 1640 cm−1 modes, a large number of vibrational degrees of freedom are Franck–Condon coupled to the electronic transition. After exposure of the explicit vibrational progressions, the residual absorptionlinewidth is separated into its homogeneous [350 cm−1 half‐width at half‐maximum (HWHM)] and inhomogeneous (313 cm−1 HWHM) components through an analysis of the absolute Raman cross sections. The value of the electronic dephasing time derived from this study (25 fs) compares well to previously published results. These data should be valuable in multimode modeling of femtosecond experiments on Nile blue.