Ultraviolet spectroscopy of the G- and S-type lignin subunits, guaiacol (G) and syringol (S), along with their para-methylated derivatives 4-methylguaiacol (4-MG) and 4-methylsyringol (4-MS), has been carried out in the cold, isolated environment of a supersonic jet. The excitation spectra and dispersed fluorescence (DFL) spectra of G and 4-MG show strong S0-S1 origins and Franck-Condon activity involving both the ring modes typical of aromatic derivatives, and the four lowest frequency out-of-plane modes (a") and lowest in-plane mode (a') involving the OH and OCH3 groups. The four low-frequency out-of-plane modes undergo extensive Duschinsky mixing between the ground and excited state. In 4-MG, combination bands involving methyl rotor levels with out-of-plane modes appeared with surprisingly high intensity, indicating a high degree of hindered rotor-vibration coupling in both S0 and S1. These mixing effects accompany the change in geometry upon π-π∗ electronic excitation going from a planar ground state to a non-planar excited state. Time-dependent density functional theory (TDDFT M05-2X∕6-311++G(d,p)) calculations predict a geometric distortion along the out-of-plane oxygen flapping coordinate, yielding a double minimum potential in S1 with a barrier to planarity of 195 cm(-1) in G. The excitation spectrum of S and 4-MS showed a much higher degree of spectral congestion and a larger geometry change evident by a shifted intensity distribution peaking ∼300 cm(-1) above the electronic origin. TDDFT calculations predict a larger geometry change in S compared with G, with the OH and H-bonded methoxy groups displaced in opposite directions above∕below the ring plane. Dispersed fluorescence from all S1 excited state levels in S∕4-MS yield only broad emission peaking far to the red of the excitation wavelength (-4500 cm(-1)). Several hypotheses regarding the source of this broad, redshifted emission were tested, but the cause remains unclear. p-Methylation was found to significantly redshift the UV absorption in both 4-MG and 4-MS, and methyl rotor transitions were assigned in both allowing for the determination of the shape and barrier heights of their respective potentials. These results provide a foundation for the discrimination of G- and S-chromophores in lignin oligomers, and demonstrate the potential for site-selective absorption.

Energy transfer in photosynthesis occurs as electronic excitations of coupled chromophores interact with their environment. The microscopic nature of these motions can enable novel energy-transfer mechanisms if the motions are not random. This study reveals synchronized and correlated fluctuations of the states within a photosynthetic pigment-protein complex, which explains prior observations of long-lived quantum coherence. SUMMARYEarly reports of long-lived quantum beating signals in photosynthetic pigmentprotein complexes were interpreted to suggest that electronic coherence benefits from protection by the protein, but many subsequent studies have suggested instead that vibrational or vibronic contributions are responsible for the observed signals. Here, we devised two 2D-spectroscopy methods to observe how each exciton is perturbed by its nuclear environment in a photosynthetic complex. The first approach simultaneously monitors each exciton's energy fluctuations over time to obtain its time-dependent electronic-nuclear interactions. The second method isolates evidence of coupled interexcitonic environmental motions. The techniques are validated with Nile Blue A and subsequently used on the Fenna-Matthews-Olson (FMO) complex. The FMO data reveal that each exciton experiences nearly identical spectral motion after excitation and that spectral motion of one excited exciton induces similar motion on unpopulated neighboring excitonic states. These synchronized and correlated spectral dynamics prolong coherences in the FMO complex after femtosecond excitation.

Cyanobacterial phycobilisome complexes absorb visible sunlight and funnel photogenerated excitons to the photosystems where charge separation occurs. In the phycobilisome complex of Synechococcus elongatus PCC 7942, phycocyanin protein rods that absorb bluer wavelengths are assembled on allophycocyanin cores that absorb redder wavelengths. This arrangement creates a natural energy gradient toward the reaction centers of the photosystems. Here, we employ broadband pump–probe spectroscopy to observe the fate of excess excitations in the phycobilisome complex of this organism. We show that excess excitons are quenched through exciton–exciton annihilation along the phycocyanin rods prior to transfer to the allophycocyanin cores. Our observations are especially relevant in comparison to other antenna proteins, where exciton annihilation primarily occurs in the lowest-energy chlorophylls. The observed effect could play a limited photoprotective role in physiological light fluences. The exciton decay dynamics is faster in the intact phycobilisome than in isolated C-phycocyanin trimers studied in earlier work, confirming that this effect is an emergent property of the complex assembly. Using the obtained annihilation data, we calculate exciton hopping times of 2.2–6.4 ps in the phycocyanin rods. This value agrees with earlier FRET calculations of exciton hopping times along phycocyanin hexamers by Sauer and Scheer.

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