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Resonance Raman spectra of the anion and cation radicals of bacterial photosynthetic pigments

Journal Article · · Journal of Physical Chemistry; (United States)
DOI:https://doi.org/10.1021/j100100a013· OSTI ID:6669755
;  [1]
  1. Univ. of California, Riverside, CA (United States)
Resonance Raman (RR) spectra are reported for the radical ions of the bacterial photosynthetic pigments bacteriochlorophyll a (BCh) and its metal-free analog bacteriopheophytin a (BPh). The radical anions, BCh[sup [minus]] and BPh[sup [minus]], were the primary focus of the RR study; however, the radical cation, BCh[sup +], was also examined. The RR data for all the radical species were acquired by using a variety of excitation wavelengths in the UV-violet region. Data were also obtained for BCh[sup +] and BCh[sup [minus]] in solvents in which the MG(II) ion axially coordinates either one or two solvent molecules. The RR data for the radical ions suggest that oxidation/reduction results in characteristic frequency shifts for the carbonyl and ring skeletal modes of the bacteriochlorin macrocycles. These frequency shifts provide benchmarks for the characterization of transient radicals in vivo via time-resolved vibrational spectroscopy. The oxidation/reduction-induced frequency shifts observed for BPh and BCh are indicative of significant structural and/or electronic perturbations of the bacteriochlorin macrocycle. 39 refs., 9 figs., 2 tabs.
OSTI ID:
6669755
Journal Information:
Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 98:49; ISSN JPCHAX; ISSN 0022-3654
Country of Publication:
United States
Language:
English