Journal of Physical Chemistry A, Vol.122, No.42, 8308-8319, 2018
Probing Dynamics in Higher-Lying Electronic States with Resonance-Enhanced Femtosecond Stimulated Raman Spectroscopy
Femtosecond stimulated Raman scattering (FSRS) measurements typically probe the structural dynamics of a molecule in the first electronically excited state, S-1. While these measurements often rely on an electronic resonance condition to increase signal strength or enhance species selectivity, the effects of the resonance condition are usually neglected. However, mode-specific enhancements of the vibrational transitions in an FSRS spectrum contain detailed information about the resonant (upper) electronic state. Analogous to ground-state resonance Raman spectroscopy, the relative intensities of the Raman bands reveal displacements of the upper potential energy surface due to changes in the bonding pattern upon S-n <- S-1 electronic excitation, and therefore provide a sensitive probe of the ultrafast dynamics in the higher-lying state, S-n. Raman gain profiles from the wavelength-dependent FSRS spectrum of the model compound 2,5-diphenylthiophene (DPT) reveal several modes with large displacement in the upper potential energy surface, including strong enhancement of a delocalized C-S-C stretching and ring deformation mode. The experimental results provide a benchmark for comparison with calculated spectra using time-dependent density functional theory (TD-DFT) and equation-of-motion coupled-cluster theory with single and double excitations (EOM-CCSD), where the calculations are based on the time-dependent formalism for resonance Raman spectroscopy. The simulated spectra are obtained from S-1-S-n transition strengths and the energy gradients of the upper (S-n) potential energy surfaces along the S-1 normal mode coordinates. The experimental results provide a stringent test of the computational approach, and indicate important limitations based on the level of theory and basis set. This work provides a foundation for making more accurate assignments of resonance-enhanced excited-state Raman spectra, as well as extracting novel information about higher-lying excited states in the transient absorption spectrum of a molecule.