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Ultrafast Time-resolved Near-IR Stimulated Raman Measurements of Functional π-conjugate Systems
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Spectroscopic Investigation of the Carotenoid Deoxyperidinin: Direct Observation of the Forbidden S0 → S1 Transition
Jordan A Greco1, Amy M LaFountain1, Naoto Kinashi2
1Department of Chemistry, University of Connecticut , 55 North Eagleville Road, Storrs, Connecticut 06269-3060, United States.
Abstract:
This paper presents a spectroscopic investigation of deoxyperidinin, a synthetic peridinin analogue in which the carbonyl functional group in peridinin was replaced by a nonconjugated methylene group. Steady-state and ultrafast time-resolved absorption and fluorescence spectroscopic experiments are carried out on deoxyperidinin in n-hexane and acetonitrile at room temperature and in 2-methyltetrahydrofuran at 77 K. The spectra of deoxyperidinin have higher vibronic resolution compared to those of peridinin. The higher resolution is due to a substantial reduction in both molecular conformational disorder and inhomogeneous broadening of the spectra of deoxyperidinin compared to peridinin. Features in the steady-state absorption spectrum of deoxyperidinin that are not evident in the spectrum of peridinin are unambiguously assigned to the forbidden S0 (1(1)Ag(-)) → S1 (2(1)Ag(-)) absorption transition. The characteristics of both the steady-state and time-resolved spectra are interpreted using EOM-CCSD, SAC-CI, and MNDO-PSDCI quantum computational formalisms that provided a theoretical framework for understanding the photophysical properties of the molecules.
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