Unraveling the Mechanism of Photoinduced Charge Transfer in Carotenoid–Porphyrin–C 60 Molecular Triad

Manna, Arun K.; Balamurugan, D.; Cheung, Margaret S.; Dunietz, Barry D.

doi:10.1021/acs.jpclett.5b00074

Unraveling the Mechanism of Photoinduced Charge Transfer in Carotenoid–Porphyrin–C ₆₀ Molecular Triad

Journal Article · Tue Mar 17 00:00:00 EDT 2015 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.5b00074· OSTI ID:1358250

Manna, Arun K. ^[1]; Balamurugan, D. ^[2]; Cheung, Margaret S. ^[3]; Dunietz, Barry D. ^[4]

Kent State Univ., Kent, OH (United States). Dept. of Chemistry; University of Houston
Univ. of Houston, TX (United States). Dept. of Physics; Univ. of Chicago, IL (United States). Computation Inst.
Univ. of Houston, TX (United States). Dept. of Physics; Rice Univ., Houston, TX (United States). Center for Theoretical Biological Physics
Kent State Univ., Kent, OH (United States). Dept. of Chemistry

Photoinduced charge transfer (CT) plays a central role in biologically significant systems and in applications that harvest solar energy. We investigate the relationship of CT kinetics and conformation in a molecular triad. The triad, consisting of carotenoid, porphyrin, and fullerene is structurally flexible and able to acquire significantly varied conformations under ambient conditions. With an integrated approach of quantum calculations and molecular dynamics simulations, we compute the rate of CT at two distinctive conformations. The linearly extended conformation, in which the donor (carotenoid) and the acceptor (fullerene) are separated by nearly 50 Å, enables charge separation through a sequential CT process. A representative bent conformation that is entropically dominant, however, attenuates the CT, although the donor and the acceptor are spatially closer. Our computed rate of CT at the linear conformation is in good agreement with measured values. Our work provides unique fundamental understanding of the photoinduced CT process in the molecular triad.

Research Organization:: Univ. of Houston, TX (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

DOE Contract Number:: SC0004832; SC0004924; AC02-05CH11231

OSTI ID:: 1358250

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 7 Vol. 6; ISSN 1948-7185

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

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