Carotenoid Nuclear Reorganization and Interplay of Bright and Dark Excited States

Elliot J. Taffet, Benjamin G. Lee, Zi S.D. Toa, Natalie Pace, Garry Rumbles, June Southall, Richard J. Cogdell, Gregory D. Scholes

Research output: Contribution to journalArticle

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.

Original languageEnglish
Pages (from-to)8628-8643
Number of pages16
JournalJournal of Physical Chemistry B
Volume123
Issue number41
DOIs
Publication statusPublished - Oct 17 2019

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carotenoids
Carotenoids
Excited states
excitation
Energy gap
photothermal deflection spectroscopy
Photoexcitation
dark energy
photoexcitation
perturbation theory
Spectroscopy
Geometry
geometry

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Cite this

Taffet, E. J., Lee, B. G., Toa, Z. S. D., Pace, N., Rumbles, G., Southall, J., ... Scholes, G. D. (2019). Carotenoid Nuclear Reorganization and Interplay of Bright and Dark Excited States. Journal of Physical Chemistry B, 123(41), 8628-8643. https://doi.org/10.1021/acs.jpcb.9b04027

Carotenoid Nuclear Reorganization and Interplay of Bright and Dark Excited States. / Taffet, Elliot J.; Lee, Benjamin G.; Toa, Zi S.D.; Pace, Natalie; Rumbles, Garry; Southall, June; Cogdell, Richard J.; Scholes, Gregory D.

In: Journal of Physical Chemistry B, Vol. 123, No. 41, 17.10.2019, p. 8628-8643.

Research output: Contribution to journalArticle

Taffet, EJ, Lee, BG, Toa, ZSD, Pace, N, Rumbles, G, Southall, J, Cogdell, RJ & Scholes, GD 2019, 'Carotenoid Nuclear Reorganization and Interplay of Bright and Dark Excited States', Journal of Physical Chemistry B, vol. 123, no. 41, pp. 8628-8643. https://doi.org/10.1021/acs.jpcb.9b04027
Taffet, Elliot J. ; Lee, Benjamin G. ; Toa, Zi S.D. ; Pace, Natalie ; Rumbles, Garry ; Southall, June ; Cogdell, Richard J. ; Scholes, Gregory D. / Carotenoid Nuclear Reorganization and Interplay of Bright and Dark Excited States. In: Journal of Physical Chemistry B. 2019 ; Vol. 123, No. 41. pp. 8628-8643.
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