Vibrational analysis of the S2→S1 fluorescence of azulene in a naphthalene mixed crystal at 4.2 K

Abstract

The S₂→S₁ fluorescence of azulene in a naphthalene mixed crystal has been measured from 740 to 1000 nm at 4.2 K. Of the 25 in‐plane fundamentals (exclusive of C–H stretches) of the S₁ state, 20 are readily identifiable in emission. A number of other bands are present in the spectrum and these are tentatively identified as S₁ out‐of‐plane vibrations induced by vibronic coupling to σπ* and/or πσ* excited electronic states. An emission previously assigned as T₁→S₀ phosphorescence is shown to be a combination band of S₂→S₁ fluorescence. The branching ratio of S₂ →S₀ fluorescence to S₂→S₁ fluorescence is approximately 7500 for xenon arc lamp excitation; this is an order of magnitude larger than the value reported for short pulse laser excitation. A summary of photophysical parameters for the low‐lying electronic states of azulene, based on the most recent and reliable experimental data, is also presented.