Initial excited state structural dynamics of lumiflavin upon ultraviolet excitation

Abstract

Excited state photophysics of flavin compounds has attracted great attention due to their involvement in several photobiological processes as a cofactor in photoreceptor enzymes. In this work, we have determined the initial excited state structural dynamics of flavin related compound, lumiflavin (LF), upon ultraviolet (UV) excitation through resonance Raman intensity analysis. A quantitative measurement of resonance Raman cross-sections across the 265 nm absorption band (257–275 nm) of LF have been performed, and Raman excitation profiles (REPs) are constructed for all the Raman active modes. The REPs and absorption cross sections have been simulated using time-dependent wave packet propagation (TDWP) formalism to extract the ultrafast dynamics of LF within 50 fs after photoexcitation. The total internal reorganization energy is estimated to be 470 cm−1, which is clear evidence for the significant structural distortion in the excited state from that of the ground state. By comparing the excited state structural changes between S1 state and 265 nm excited state, we found that different molecular distortions occur following photoexcitation to those two different states. The total reorganization energy is obtained to be 1542 cm−1, in which the maximum contribution comes from the inertial response of water (1070 cm−1). Additionally, our simulation also yields an instantaneous response of the first solvation shell within an ultrafast timescale, τ ∼ 30 fs, following photoexcitation. The current study provides the basis for future investigations to determine the excited state properties of flavin compounds upon UV excitations.