RESONANCE RAMAN STUDIES ON EXCITED STATES OF ZN($\Pi$) OCTAETHYLPORAPHYRIN

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1994

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Ohio State University

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The important biological process of charge separation in the photosynthetic reaction center is initiated by photoexcitation of a chlorophyll molecule into the excited singlet state ($S_{1}$). To better understand this process, more insight into the electronic structure and conformation of singlet excited porphyring is essential. Picosecond time resolved pump-probe Resonance Raman scattering can provide this insight by means of probing bond strengths in the molecule in the excited state. For the experiments we selected zn($\Pi$) Octachylporphyrin (ZnOEP) because it has several characteristics beneficial for the experiment. In the $S_{1}$ state the resonance Raman spectrum is dominated by totally symmetric modes at 1564, 1450, 1359, 1261, 1135 and $664 cm^{-1}$. Since nontotally symmetric modes are only weakly enbaneed, we conclude that Jahn-Teller distortion is absent in this state. In the lowest triplet state ($T_{1}$) nontotally symmetric modes dominate the spectrum. Jahn-Teller distortion in the triplet state thus appears to be important. The latter conclusion aggress with previous results on triplet states that indicated Jahn-Teller distortion in metalloporphyrins with $D_{4h}$ symmetry, Implications of our results for the efficiency of charge separation in the photosynthetic reaction center will be discussed. (Supported by NIH grant GM25480)

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Author Institution: Departments of Chemistry and the LASER Laboratory, Michigan State University

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