Coherent Vibrational Spectrum via Time-Resolved Fluorescence for Molecular Dynamics and Identification of Emitting Species-Application to Excited-State Intramolecular Proton Transfer.

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.

Identification of an emitting molecular species by time-resolved fluorescence applied to the excited state dynamics of pigment yellow 101.

Time-resolved fluorescence (TRF) with a resolution higher than the periods of vibrations may provide the vibrational spectrum of an emitting species by directly recording the vibrational wave packet motions in time. We applied high-resolution TRF to investigate the excited-state dynamics of pigment yellow 101 (P.Y.101). The TRF spectra of P.Y.101 in dichloromethane showed that upon photoexcitation of the enol isomer, dynamics occur in the S1 state to form a product in two time constants at 30 and 140 fs. TRF signals were modulated due to the vibrational wave packet motions in the excited states, which provided the vibrational spectra of the emitting species. Depending on the emission wavelength, two different vibrational spectra were evident. With the help of theoretical calculations, the two spectra were assigned to the enol and keto isomers of P.Y.101 in the S1 state, leading to the conclusion that P.Y.101 undergoes ultrafast excited-state intramolecular proton transfer (ESIPT) with a quantum yield close to 1. Visible-pump infrared-probe transient absorption spectra were recorded to corroborate this conclusion.