@article{eb5b68c2c9874b01986310dd5f78e153,
title = "Carotenoid Nuclear Reorganization and Interplay of Bright and Dark Excited States",
abstract = "We report quantum chemical calculations using multireference perturbation theory (MRPT) with the density matrix renormalization group (DMRG) plus photothermal deflection spectroscopy measurements to investigate the manifold of carotenoid excited states and establish their energies relative to the bright state (S2) as a function of nuclear reorganization. We conclude that the primary photophysics and function of carotenoids are determined by interplay of only the bright (S2) and lowest-energy dark (S1) states. The lowest-lying dark state, far from being energetically distinguishable from the lowest-lying bright state along the entire excited-state nuclear reorganization pathway, is instead computed to be either the second or first excited state depending on what equilibrium geometry is considered. This result suggests that, rather than there being a dark intermediate excited state bridging a non-negligible energy gap from the lowest-lying dark state to the lowest-lying bright state, there is in fact no appreciable energy gap to bridge following photoexcitation. Instead, excited-state nuclear reorganization constitutes the bridge from S2 to S1, in the sense that these two states attain energetic degeneracy along this pathway.",
author = "Taffet, {Elliot J.} and Lee, {Benjamin G.} and Toa, {Zi S.D.} and Natalie Pace and Garry Rumbles and June Southall and Cogdell, {Richard J.} and Scholes, {Gregory D.}",
note = "Funding Information: G.R. and G.D.S. acknowledge support from the Bioinspired Light-Escalated Chemistry Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award DE-SC0019370. E.J.T. was supported by the Belgian American Educational Foundation and is grateful to David Beljonne for fruitful discussions. E.J.T. thanks Garry Rumbles and his group at the National Renewable Energy Lab for supporting his visit. R.J.C. and J.S. acknowledge support from the Photosynthetic Antenna Research Center (PARC), Energy Frontier Research Center funded by the Department of Energy, Office of Science, Office of Basic Energy Sciences (DE-SC0001035). Funding Information: G.R. and G.D.S. acknowledge support from the Bioinspired Light-Escalated Chemistry Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award DE-SC0019370. E.J.T. was supported by the Belgian American Educational Foundation and is grateful to David Beljonne for fruitful discussions. E.J.T. thanks Garry Rumbles and his group at the National Renewable Energy Lab for supporting his visit. R.J.C. and J.S. acknowledge support from the Photosynthetic Antenna Research Center (PARC), Energy Frontier Research Center funded by the Department of Energy, Office of Science, Office of Basic Energy Sciences (DE-SC0001035). Publisher Copyright: Copyright {\textcopyright} 2019 American Chemical Society.",
year = "2019",
month = oct,
day = "17",
doi = "10.1021/acs.jpcb.9b04027",
language = "English (US)",
volume = "123",
pages = "8628--8643",
journal = "Journal of Physical Chemistry B",
issn = "1089-5647",
number = "41",
}