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

Journal Article · · Journal of Physical Chemistry Letters
 [1];  [2];  [3];  [4]
  1. Kent State Univ., Kent, OH (United States). Dept. of Chemistry; University of Houston
  2. Univ. of Houston, TX (United States). Dept. of Physics; Univ. of Chicago, IL (United States). Computation Inst.
  3. Univ. of Houston, TX (United States). Dept. of Physics; Rice Univ., Houston, TX (United States). Center for Theoretical Biological Physics
  4. Kent State Univ., Kent, OH (United States). Dept. of Chemistry
+ Show Author Affiliations
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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Related Subjects

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION
molecular dynamics
molecular triad
organic photovoltaic
photoinduced charge transfer
range-separated hybrid functional
solvation