Qy-excitation resonance Raman spectra of chlorophyll a and bacteriochlorophyll c/d aggregates. Effects of peripheral substituents on the low-frequency vibrational characteristics.

Low-frequency (80-700 cm-1) Qy-excitation resonance Raman (RR) spectra are reported for thin-solid-film aggregates of several chlorophyll (Chl) a and bacteriochlorophyll (BChl) c/d pigments. The pigments include Chl a, pyrochlorophyll a (PChl a), methylpyrochloropyllide a (MPChl a), methylbacteriochloropyllide d (MBChl d), [E,M] BChl cS, [E,E] BChl cF, and [P,E] BChl cF. The BChl c/d's are the principal constituents of the chlorosomal light-harvesting apparatus of green photosynthetic bacteria. Together, the various Chl a's and BChl c/d's represent a series in which the peripheral substituent groups on the chlorin macrocycle are varied in systematic fashion. All of the Chl a and BChl c/d aggregates exhibit rich low-frequency vibrational patterns. In the case of the BChl c/d's, certain modes in the very low-frequency region (100-200 cm-1) experience exceptionally strong Raman intensity enhancements. The frequencies of these modes are qualitatively similar to those of oscillations observed in femtosecond optical experiments on chlorosomes. The RR data indicate that the low-frequency vibrations are best characterized as intramolecular out-of-plane deformations of the chlorin macrocycle rather than intermolecular modes. The coupling of the out-of-plane modes in turn implies that the Qy electronic transition(s) of the aggregate have out-of-plane character. The RR spectra of the BChl c/d's also reveal that the nature of the alkyl substituents at the 8 and 12 positions of the macrocycle plays an important role in determining the detailed features of the low-frequency vibrational patterns. The frequencies of the modes are particularly sensitive to larger substituent groups whose conformations may be more easily perturbed in the tightly packed aggregates. These factors also make aggregates of pigments containing larger substituents more susceptible to structural, electronic, and vibrational inhomgeneities. Collectively, the RR studies of the various pigments delineate the factors which influence the low-frequency vibrational characteristics of chlorosomal aggregates.