Signature of electronically excited states in Raman spectra of azobenzene derivatives. Computational and experimental approaches

Raman spectroscopy can provide highly sensitive and detailed information about the structural fingerprint of molecules, enabling their identification. In this study, our aim is to understand the enhanced intensity observed in experimental Raman measurements. Five azobenzene derivatives were selected, each substituted with different functional groups, for both experimental and theoretical investigations. To reproduce the experimental trend, we employed various levels of theory using the QM-DFT approach. Theoretical results were compared to experimental data through both qualitative and quantitative analyses. A good correlation between theoretical and experimental results was achieved when considering electronic transitions to predict the theoretical Raman spectra and interpret the experimental data. Our theoretical results indicate that even dark (n pi*) transitions, which are forbidden and have an oscillator strength close to zero, can have a signature in the Raman spectra due to the resonance effect with incident energy. Additionally, the vibrational modes stimulated by the presence of itit* bright states, being at the pre-resonance with the incident energy, was clearly separated from the vibrational frequencies of the dark states, which was evinced in the Raman fingerprint. Theoretical Raman spectra of azobenzene derivatives, substituted with push-pull moieties, revealed contributions from the charge transfer transitions (nit*CT, itit*CT) as well as back-donation of electron density, observed for the first time in an azobenzene derivative. Our protocol, proposing a quantitative and qualitative overlap between theoretical and experimental data, confirms the presence of combination modes between vibrational levels and electronically excited states.