Time-resolved fluorescence (TF) with high-enough resolution
enables
recording of a coherent vibrational spectrum (CVS). Because a CVS
attained via TF (CVSF) is descended from the frequency modulation
of the fluorescence spectrum, it gives the vibrational spectrum of
the emitting state. Therefore, CVSF can be a powerful tool for the
identification of an emitting state along with the investigation of
molecular dynamics in excited states. Herein, we report CVSF of a
Schiff base salicylaldehyde azine (SAA) that has two possible excited-state
intramolecular proton transfer (ESIPT) sites. The ESIPT time of SAA
in dichloromethane is determined to be 22 fs. Quantitative agreement
between the experimental CVSF and calculated CVSF of the mono-keto
isomer demonstrates that ESIPT indeed occurs in SAA only on one side.
More importantly, we show that a CVSF can be utilized to identify
an emitting species and its state with the help of quantum chemical
calculations. Implications of the CVSF obtained by assuming impulsive
excitation of vibrations are discussed in terms of the molecular mechanism
of ESIPT and the generation of nuclear wave packets in the product
state.