Excitation-Dependence of Excited-State Dynamics and Vibrational Relaxation of Lutein Explored by Multiplex Transient Grating

Multiplex transient grating (MTG) spectroscopy was applied to lutein in ethanol to investigate the excitation-energy dependence of the excited-state dynamics and vibrational relaxation. The transient spectra obtained upon low (480 nm) and high-energy (380 nm) excitation both recorded a strong excited-state absorption (ESA) of S₁ → S as well as a broad band in the blue wavelength that was previously proposed as the S* state. By means of Gaussian decomposition and global fitting of the ESA band, a long-time component assigned to the triplet state was derived from the kinetic trace of 480 nm excitation. Moreover, the MTG signal with a resolution of 110 fs displayed the short-time quantum beat signal. In order to unveil the vibrational coherence in the excited-state decay, the linear and non-linear simulations of the steady spectrum and dynamic signals were presented in which at least three fundamental modes standing for C-C stretching (ν₁), C=C stretching (ν₂), and O-H valence vibrations (ν₃) were considered to analyze the experimental signals. It was identified that the vibrational coherence between ν₁ and ν₃ or ν₂ and ν₃ was responsible for quantum beat that may be associated with the triplet state. We concluded that upon low- or high-energy excitation into the S₂ state, the photo-isomerization of the molecule and structural recovery on the time-scale of vibrational cooling are the key factors to form a mixed conformation in the hot-S₁ state that is the precursor of a long life-time triplet.