Time-Resolved Femtosecond Stimulated Raman Spectra and DFT Anharmonic Vibrational Analysis of an Electronically Excited Rhenium Photosensitizer.

Time-resolved femtosecond stimulated Raman spectra (FSRS) of a prototypical organometallic photosensitizer/photocatalyst ReCl(CO)(3) (2,2'-bipyridine) were measured in a broad spectral range, similar to 40-2000 (4000) cm(-1) at time delays from 40 fs to 4 ns after 400 nm excitation of the lowest allowed electronic transition. Theoretical ground- and excited-state Raman spectra were obtained by anharmonic vibrational analysis using second-order vibrational perturbation theory on vibrations calculated by harmonic approximation at density functional theory-optimized structures. A good match with anharmonically calculated vibrational frequencies allowed for assigning experimental Raman features to particular vibrations. Observed frequency shifts upon excitation (nu(ReCl) and v(CC inter-ring) vibrations upward; nu(CC, CN) and nu(Re-C) downward) are consistent with the bonding/antibonding characters of the highest occupied molecular orbital and the lowest unoccupied molecular orbital involved in excitation and support the delocalized formulation of the lowest triplet state as ReCl(CO)(3) -> bpy charge transfer. FSRS spectra show a mode-specific temporal evolution, providing insights into the intersystem crossing (ISC) mechanism and subsequent relaxation. Most of the Raman features are present at , similar to 40 fs and exhibit small shifts and intensity changes with time. The 1450-1600 cm(-1) group of bands due to CC, CN, and CC (inter-ring) stretching vibrations undergoes extensive restructuring between 40 and similar to 150 fs, followed by frequency upshifts and a biexponential (0.38, 21 ps) area growth, indicating progressing charge separation in the course of the formation and relaxation of the lowest triplet state. Early (40-150 fs) restructuring was also observed in the low-frequency range for nu(Re-Cl) and delta(Re-C-O) vibrations that are presumably activated by ISC. FSRS experimental innovations employed to measure low- and high-energy Raman features simultaneously are described and discussed in detail.