Peridinin Torsional Distortion and Bond-Length Alternation Introduce Intramolecular Charge-Transfer and Correlated Triplet Pair Intermediate Excited States

The Journal of Physical Chemistry. B
Elliot J Taffet, Gregory D Scholes

Abstract

The nature of intramolecular charge transfer (ICT) and the mechanism of intramolecular singlet fission (SF) in peridinin remain open research questions. Obtaining an understanding of the population evolution from the bright state to dark state following a photoinduced electronic transition is critical. Unambiguously describing this evolution in peridinin, and light-harvesting carotenoids in general, has proven elusive experimentally and computationally. To offer a balanced description of the bright- and dark-state electronic structures, we here apply ab initio multireference perturbation theory quantum chemistry-the density matrix renormalization group self-consistent field and complete-active-space self-consistent field with second-order N-electron valence perturbation theory. At traditional bright- (S2) and dark-state (S1) optimized geometries, we find that an additional correlated triplet pair state and ICT state are derived from the canonical polyene Bu (S3) and 3Ag (S4) dark singlet excited states, respectively. Whereas the S3 state's physical properties are insensitive to peridinin's allene-tail donor and lactone ring acceptor functionalization, the S4 state exhibits a markedly enhanced oscillator strength and highest occ...Continue Reading

References

Mar 1, 1996·Photochemistry and Photobiology·H A Frank, R J Cogdell
Oct 1, 1993·Physical Review. B, Condensed Matter·S R White
Nov 9, 1992·Physical Review Letters·S R White
Nov 6, 1995·Physical Review Letters·S Östlund, S Rommer
Jan 5, 2000·Biophysical Journal·F J KleimaH van Amerongen
Feb 28, 2001·Proceedings of the National Academy of Sciences of the United States of America·C C GradinaruR van Grondelle
Apr 12, 2001·Plant Physiology·P MüllerK K Niyogi
Dec 18, 2002·Proceedings of the National Academy of Sciences of the United States of America·Donatas ZigmantasTomas Polivka
Apr 15, 2004·Chemical Reviews·Tomás Polívka, Villy Sundström
Jul 23, 2004·The Journal of Chemical Physics·Garnet Kin-Lic Chan
Dec 8, 2004·Biochemistry·Emmanouil PapagiannakisRienk van Grondelle
Jan 11, 2005·The Journal of Chemical Physics·Gerrit MoritzMarkus Reiher
Aug 12, 2005·Chemical Reviews·Jacopo TomasiRoberto Cammi
Nov 19, 2005·The Journal of Chemical Physics·Gerrit MoritzMarkus Reiher
Jul 21, 2006·The Journal of Physical Chemistry. B·Lavanya PremvardhanRienk van Grondelle
Nov 14, 2006·Archives of Biochemistry and Biophysics·Tomás PolívkaHarry A Frank
Nov 1, 2007·Photosynthesis Research·S MackowskiC Bräuchle
Apr 17, 2008·The Journal of Chemical Physics·Dominika Zgid, Marcel Nooijen
Apr 17, 2008·The Journal of Chemical Physics·Debashree GhoshGarnet Kin-Lic Chan
Feb 5, 2009·The Journal of Chemical Physics·Martin KleinschmidtStefan Grimme
May 27, 2009·The Journal of Chemical Physics·Dominika ZgidGarnet Kin-Lic Chan
Sep 25, 2009·Chemical Physics Letters·Nirmalya ChatterjeeHarry A Frank
Oct 3, 2009·Organic Letters·Takayuki KajikawaShigeo Katsumura
Nov 26, 2009·Proceedings of the National Academy of Sciences of the United States of America·Tim SchulteHarry A Frank
Aug 27, 2010·The Journal of Physical Chemistry. a·Evgeny E OstroumovAlfred R Holzwarth
Sep 10, 2010·The Journal of Physical Chemistry. B·Miriam M EnriquezHarry A Frank
Jan 12, 2011·The Journal of Physical Chemistry. B·Tammie NelsonSergei Tretiak
Jan 12, 2011·Annual Review of Physical Chemistry·Garnet Kin-Lic Chan, Sandeep Sharma
Mar 31, 2006·Chemical Physics·Toshiyuki KusumotoHideki Hashimoto
Apr 2, 2011·The Journal of Physical Chemistry. B·Marcel FucimanHarry A Frank

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Citations

Mar 19, 2020·Journal of the Royal Society, Interface·Elliot J TaffetGregory D Scholes
Dec 6, 2018·Journal of Photochemistry and Photobiology. B, Biology·Zi S D ToaGregory D Scholes
Sep 26, 2019·The Journal of Physical Chemistry. B·Elliot J TaffetGregory D Scholes

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