Transient absorption, femtosecond dynamics, vibrational coherence and molecular modelling of the photoisomerization of N-salicylidene-o-aminophenol in solution

TL;DR

This study combines femtosecond transient absorption spectroscopy and theoretical calculations to elucidate the excited state relaxation, vibrational coherence, and photoisomerization mechanisms of N-salicylidene-o-aminophenol in ethanol.

Contribution

It provides a detailed understanding of the vibronic coupling and vibrational modes involved in the photoisomerization process of SOAP, integrating experimental and computational insights.

Findings

Identification of two tautomer interconversions via ESIPT

Observation of vibrational coherence modulating the transient absorption signals

Elucidation of vibrational modes involved in excited state dynamics

Abstract

This article presents a study of the excited state relaxation dynamics of N-salycylidene-o-aminophenol (SOAP) in ethanol solution. Femtosecond transient absorption (TA) spectroscopy and theoretical calculations are used in combination to establish the mechanism of the excited state relaxation and type of molecular species involved in the accompanying phototransformations. TA spectra show that upon photoexcitation two SOAP tautomers (E-enol and Z-keto) interconvert by ESIPT. The molecule can subsequently isomerize to the E-keto form of SOAP. An intriguing observation is that the TA spectra of this compound in ethanol show modulations of the signal at the stimulated emission spectral range. It is found that these modulations are due to the coherence of the excited ensemble of molecules whose evolution over time represents a moving wave packet. After Fourier transform of the modulations, two characteristic frequencies are identified. These frequencies are referred to the corresponding vibrational modes of the excited state and their nature is elucidated by DFT quantum chemical calculations. The obtained experimental and theoretical data reveal the nature of vibronic coupling between the ground and excited state and the type of molecular vibrations involved in the molecular dynamics along the potential surface of the first excited state at the initial moment right after excitation. These vibrations characterize the starting point in the excited state dynamics of the molecule toward Z-E isomerization of the keto form of SOAP. The study provides a comprehensive picture of the dynamic processes taking place upon photoexcitation of the compound, which might enable control over the various relaxation channels.