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.

doi:10.1021/acs.jpcb.9b04027

Carotenoid Nuclear Reorganization and Interplay of Bright and Dark Excited States

Journal Article · Wed Sep 25 04:00:00 EDT 2019 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

DOI:https://doi.org/10.1021/acs.jpcb.9b04027· OSTI ID:1597296

^[1]; Lee, Benjamin G. ^[2]; ^[3]; Pace, Natalie ^[2]; ^[2]; Southall, June ^[4]; Cogdell, Richard J. ^[4]; ^[3]

Princeton Univ., NJ (United States); Princeton University
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Princeton Univ., NJ (United States)
Univ. of Glasgow, Scotland (United Kingdom)

We report here 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 finding 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.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Bioinspired Light-Escalated Chemistry (BioLEC); Princeton Univ., NJ (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Belgian American Educational Foundation

Grant/Contract Number:: SC0019370; SC0001035

OSTI ID:: 1597296

Alternate ID(s):: OSTI ID: 1571900

Journal Information:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Journal Name: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry Journal Issue: 41 Vol. 123; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (143)

Light-harvesting function of carotenoids in photo-synthesis: The roles of the newly found 11Bu? state Koyama, Yasushi; Rondonuwu, Ferdy S.; Fujii, Ritsuko Biopolymers, Vol. 74, Issue 1-2 https://doi.org/10.1002/bip.20034	journal	January 2004
Software update: the ORCA program system, version 4.0: Software update Neese, Frank Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 8, Issue 1 https://doi.org/10.1002/wcms.1327	journal	July 2017
P y SCF: the Python-based simulations of chemistry framework : The PySCF program Sun, Qiming; Berkelbach, Timothy C.; Blunt, Nick S. Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 8, Issue 1 https://doi.org/10.1002/wcms.1340	journal	September 2017
Nonadiabatic dynamics: The SHARC approach Mai, Sebastian; Marquetand, Philipp; González, Leticia Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 8, Issue 6 https://doi.org/10.1002/wcms.1370	journal	May 2018
The ORCA program system: The ORCA program system Neese, Frank Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 1 https://doi.org/10.1002/wcms.81	journal	June 2011
Spectroscopic Studies of the Low-Lying Singlet Excited Electronic States and Photochemical Properties of Carotenoids Frank, Harry A. Archives of Biochemistry and Biophysics, Vol. 385, Issue 1 https://doi.org/10.1006/abbi.2000.2091	journal	January 2001
Correlated wavefunction methods in bioinorganic chemistry Neese, Frank; Liakos, Dimitrios G.; Ye, Shengfa JBIC Journal of Biological Inorganic Chemistry, Vol. 16, Issue 6 https://doi.org/10.1007/s00775-011-0787-6	journal	May 2011
Four-wave mixing signals from β-carotene and its n = 15 homologue Sugisaki, Mitsuru; Fujiwara, Masazumi; Yanagi, Kazuhiro Photosynthesis Research, Vol. 95, Issue 2-3 https://doi.org/10.1007/s11120-007-9265-y	journal	October 2007
Low-lying electronic states of carotenoids DeCoster, Beverly; Christensen, Ronald L.; Gebhard, Ronald Biochimica et Biophysica Acta (BBA) - Bioenergetics, Vol. 1102, Issue 1 https://doi.org/10.1016/0005-2728(92)90070-I	journal	August 1992
A low-lying weak transition in the polyene α,ω-diphenyloctatetraene Hudson, B. S.; Kohler, B. E. Chemical Physics Letters, Vol. 14, Issue 3 https://doi.org/10.1016/0009-2614(72)80119-2	journal	June 1972
On the origin of a low-lying forbidden transition in polyenes and related molecules Schulten, K.; Karplus, M. Chemical Physics Letters, Vol. 14, Issue 3 https://doi.org/10.1016/0009-2614(72)80120-9	journal	June 1972
Direct minimization in mc scf theory. the quasi-newton method Eade, Richard H. A.; Robb, Michael A. Chemical Physics Letters, Vol. 83, Issue 2 https://doi.org/10.1016/0009-2614(81)85480-2	journal	October 1981
MC SCF gradient optimization of the H2CO→H2 + CO transition structure Schlegel, H. Bernhard; Robb, Michael A. Chemical Physics Letters, Vol. 93, Issue 1 https://doi.org/10.1016/0009-2614(82)85052-5	journal	November 1982
Direct measurement of the lowest excited singlet state lifetime of all-trans-β-carotene and related carotenoids Wasielewski, Michael R.; Kispert, Lowell D. Chemical Physics Letters, Vol. 128, Issue 3 https://doi.org/10.1016/0009-2614(86)80332-3	journal	July 1986
Raman spectra of all-trans-β-carotene in the S1 and T1 states produced by direct photoexcitation Hashimoto, Hideki; Koyama, Yasushi Chemical Physics Letters, Vol. 163, Issue 2-3 https://doi.org/10.1016/0009-2614(89)80045-4	journal	November 1989
The CC stretching Raman lines of [β-carotene isomers in the S1 state as detected by pump-probe resonance Raman spectroscopy Hashimoto, Hideki; Koyama, Yasushi Chemical Physics Letters, Vol. 154, Issue 4 https://doi.org/10.1016/0009-2614(89)85363-1	journal	January 1989
Raman spectra of all-trans-β-apo-8′-carotenal in the S1 and T1 states; a picosecond pump-and-probe technique using ML-Qs pulse trains Hashimoto, Hideki; Koyama, Yasushi Chemical Physics Letters, Vol. 162, Issue 6 https://doi.org/10.1016/0009-2614(89)87018-6	journal	October 1989
Carotenoid fluorescence Gillbro, Tomas; Cogdell, Richard J. Chemical Physics Letters, Vol. 158, Issue 3-4 https://doi.org/10.1016/0009-2614(89)87342-7	journal	June 1989
Kohn—Sham density-functional theory within a finite basis set Pople, John A.; Gill, Peter M. W.; Johnson, Benny G. Chemical Physics Letters, Vol. 199, Issue 6 https://doi.org/10.1016/0009-2614(92)85009-Y	journal	November 1992
Fluorescence from the S1(2 1Ag) state of all-trans-β-carotene Bondarev, S. L.; Knyukshto, V. N. Chemical Physics Letters, Vol. 225, Issue 4-6 https://doi.org/10.1016/0009-2614(94)87092-6	journal	August 1994
S2 → S0 fluorescence and transient Sn ← S1 absorption of all-rans-β-carotene in solid and liquid solutions Bondarev, S. L.; Bachilo, S. M.; Dvornikov, S. S. Journal of Photochemistry and Photobiology A: Chemistry, Vol. 46, Issue 3 https://doi.org/10.1016/1010-6030(89)87048-0	journal	March 1989
Excited-state dynamics among the 1Bu+, 1Bu− and 2Ag− states of all-trans-neurosporene as revealed by near-infrared time-resolved absorption spectroscopy Zhang, Jian-Ping; Inaba, Toru; Watanabe, Yasutaka Chemical Physics Letters, Vol. 332, Issue 3-4 https://doi.org/10.1016/S0009-2614(00)01275-6	journal	December 2000
N-electron valence state perturbation theory: a fast implementation of the strongly contracted variant Angeli, Celestino; Cimiraglia, Renzo; Malrieu, Jean-Paul Chemical Physics Letters, Vol. 350, Issue 3-4 https://doi.org/10.1016/S0009-2614(01)01303-3	journal	December 2001
Subpicosecond dynamics in the excited state absorption of all-trans-β-Carotene de Weerd, Frank L.; van Stokkum, Ivo H. M.; van Grondelle, Rienk Chemical Physics Letters, Vol. 354, Issue 1-2 https://doi.org/10.1016/S0009-2614(02)00095-7	journal	March 2002
Dynamics of vibrational relaxation in the S1 state of carotenoids having 11 conjugated CC bonds Hörvin Billsten, Helena; Zigmantas, Donatas; Sundström, Villy Chemical Physics Letters, Vol. 355, Issue 5-6 https://doi.org/10.1016/S0009-2614(02)00268-3	journal	April 2002
The first detection of the 3A g − state in carotenoids using resonance-Raman excitation profiles Furuichi, Kentaro; Sashima, Tokutake; Koyama, Yasushi Chemical Physics Letters, Vol. 356, Issue 5-6 https://doi.org/10.1016/S0009-2614(02)00412-8	journal	April 2002
Two different pathways of internal conversion in carotenoids depending on the length of the conjugated chain Fujii, Ritsuko; Inaba, Toru; Watanabe, Yasutaka Chemical Physics Letters, Vol. 369, Issue 1-2 https://doi.org/10.1016/S0009-2614(02)01999-1	journal	February 2003
A first detection of singlet to triplet conversion from the 11Bu− to the 13Ag state and triplet internal conversion from the 13Ag to the 13Bu state in carotenoids: dependence on the conjugation length Rondonuwu, Ferdy S.; Watanabe, Yasutaka; Fujii, Ritsuko Chemical Physics Letters, Vol. 376, Issue 3-4 https://doi.org/10.1016/S0009-2614(03)00983-7	journal	July 2003
The 2Ag− energies of all-trans-neurosporene and spheroidene as determined by fluorescence spectroscopy Fujii, Ritsuko; Onaka, Kengo; Kuki, Michitaka Chemical Physics Letters, Vol. 288, Issue 5-6 https://doi.org/10.1016/S0009-2614(98)00376-5	journal	May 1998
The 2Ag− energy of crystalline all-trans-spheroidene as determined by resonance-Raman excitation profiles Sashima, Tokutake; Shiba, Mikio; Hashimoto, Hideki Chemical Physics Letters, Vol. 290, Issue 1-3 https://doi.org/10.1016/S0009-2614(98)00481-3	journal	June 1998
A new singlet-excited state of all-trans-spheroidene as detected by resonance-Raman excitation profiles Sashima, Tokutake; Nagae, Hiroyoshi; Kuki, Michitaka Chemical Physics Letters, Vol. 299, Issue 2 https://doi.org/10.1016/S0009-2614(98)01278-0	journal	January 1999
Time-dependent density functional theory within the Tamm–Dancoff approximation Hirata, So; Head-Gordon, Martin Chemical Physics Letters, Vol. 314, Issue 3-4 https://doi.org/10.1016/S0009-2614(99)01149-5	journal	December 1999
Twin states and conical intersections in linear polyenes Fuß, W.; Haas, Y.; Zilberg, S. Chemical Physics, Vol. 259, Issue 2-3 https://doi.org/10.1016/S0301-0104(00)00200-7	journal	September 2000
The very early events following photoexcitation of carotenoids Hashimoto, Hideki; Yanagi, Kazuhiro; Yoshizawa, Masayuki Archives of Biochemistry and Biophysics, Vol. 430, Issue 1 https://doi.org/10.1016/j.abb.2004.04.022	journal	October 2004
Multidimensional spectroscopy of β-carotene: Vibrational cooling in the excited state Buckup, Tiago; Hauer, Jürgen; Möhring, Jens Archives of Biochemistry and Biophysics, Vol. 483, Issue 2 https://doi.org/10.1016/j.abb.2008.10.031	journal	March 2009
How much double excitation character do the lowest excited states of linear polyenes have? Starcke, Jan Hendrik; Wormit, Michael; Schirmer, Jochen Chemical Physics, Vol. 329, Issue 1-3 https://doi.org/10.1016/j.chemphys.2006.07.020	journal	October 2006
Quantum control spectroscopy of vibrational modes: Comparison of control scenarios for ground and excited states in β-carotene Hauer, Jürgen; Buckup, Tiago; Motzkus, Marcus Chemical Physics, Vol. 350, Issue 1-3 https://doi.org/10.1016/j.chemphys.2008.03.021	journal	June 2008
The A g + state falls below 3 A g - at carotenoid-relevant conjugation lengths Taffet, Elliot J.; Scholes, Gregory D. Chemical Physics, Vol. 515 https://doi.org/10.1016/j.chemphys.2017.12.008	journal	November 2018
Internal conversion of 1Bu+ → 1Bu− → 2Ag− and fluorescence from the 1Bu− state in all-trans-neurosporene as probed by up-conversion spectroscopy Fujii, Ritsuko; Fujino, Tatsuya; Inaba, Toru Chemical Physics Letters, Vol. 384, Issue 1-3 https://doi.org/10.1016/j.cplett.2003.11.074	journal	January 2004
The π→π* excited states of long linear polyenes studied by the CASCI-MRMP method Kurashige, Yuki; Nakano, Haruyuki; Nakao, Yoshihide Chemical Physics Letters, Vol. 400, Issue 4-6 https://doi.org/10.1016/j.cplett.2004.10.141	journal	December 2004
Low-lying singlet states of carotenoids having 8–13 conjugated double bonds as determined by electronic absorption spectroscopy Wang, Peng; Nakamura, Ryosuke; Kanematsu, Yasuo Chemical Physics Letters, Vol. 410, Issue 1-3 https://doi.org/10.1016/j.cplett.2005.05.037	journal	July 2005
Conjugation length dependence of relaxation kinetics in β-carotene homologs probed by femtosecond Kerr-gate fluorescence spectroscopy Kosumi, Daisuke; Yanagi, Kazuhiro; Fujii, Ritsuko Chemical Physics Letters, Vol. 425, Issue 1-3 https://doi.org/10.1016/j.cplett.2006.05.023	journal	July 2006
Singlet internal conversion processes in the order of 1Bu+→3Ag-→1Bu-→2Ag-→1Ag- in all-trans-spheroidene and lycopene as revealed by subpicosecond time-resolved Raman spectroscopy Rondonuwu, Ferdy S.; Kakitani, Yoshinori; Tamura, Hiroshi Chemical Physics Letters, Vol. 429, Issue 1-3 https://doi.org/10.1016/j.cplett.2006.07.061	journal	September 2006
Presence and absence of electronic mixing in shorter-chain and longer-chain carotenoids: Assignment of the symmetries of 1Bu- and 3Ag- states located just below the 1Bu+ state Sutresno, Adita; Kakitani, Yoshinori; Zuo, Ping Chemical Physics Letters, Vol. 447, Issue 1-3 https://doi.org/10.1016/j.cplett.2007.08.081	journal	October 2007
Dark excited states of carotenoids: Consensus and controversy Polívka, Tomáš; Sundström, Villy Chemical Physics Letters, Vol. 477, Issue 1-3 https://doi.org/10.1016/j.cplett.2009.06.011	journal	July 2009
Excited-state dynamics of the 1Bu+,3Ag−, and 1Bu− states in a carotenoid molecule by 5-fs absorption spectroscopy Kobayashi, T.; Nishimura, K.; Rondonuwu, F. S. Journal of Luminescence, Vol. 112, Issue 1-4 https://doi.org/10.1016/j.jlumin.2004.09.030	journal	April 2005
N -Electron Valence State Perturbation Theory Based on a Density Matrix Renormalization Group Reference Function, with Applications to the Chromium Dimer and a Trimer Model of Poly( p -Phenylenevinylene) Guo, Sheng; Watson, Mark A.; Hu, Weifeng Journal of Chemical Theory and Computation, Vol. 12, Issue 4 https://doi.org/10.1021/acs.jctc.5b01225	journal	March 2016
An Ab Initio Exciton Model Including Charge-Transfer Excited States Li, Xin; Parrish, Robert M.; Liu, Fang Journal of Chemical Theory and Computation, Vol. 13, Issue 8 https://doi.org/10.1021/acs.jctc.7b00171	journal	July 2017
Exchange Coupling Interactions from the Density Matrix Renormalization Group and N -Electron Valence Perturbation Theory: Application to a Biomimetic Mixed-Valence Manganese Complex Roemelt, Michael; Krewald, Vera; Pantazis, Dimitrios A. Journal of Chemical Theory and Computation, Vol. 14, Issue 1 https://doi.org/10.1021/acs.jctc.7b01035	journal	December 2017
Femtosecond Heterodyne Transient-Grating Studies of Nonradiative Decay of the S ₂ (1 ¹ B _u ⁺ ) State of β-Carotene: Contributions from Dark Intermediates and Double-Quantum Coherences Ghosh, Soumen; Bishop, Michael M.; Roscioli, Jerome D. The Journal of Physical Chemistry B, Vol. 119, Issue 47 https://doi.org/10.1021/acs.jpcb.5b09405	journal	November 2015
Femtosecond Heterodyne Transient Grating Studies of Nonradiative Deactivation of the S ₂ (1 ¹ B _u ⁺ ) State of Peridinin: Detection and Spectroscopic Assignment of an Intermediate in the Decay Pathway Ghosh, Soumen; Bishop, Michael M.; Roscioli, Jerome D. The Journal of Physical Chemistry B, Vol. 120, Issue 15 https://doi.org/10.1021/acs.jpcb.5b12753	journal	April 2016
Peridinin Torsional Distortion and Bond-Length Alternation Introduce Intramolecular Charge-Transfer and Correlated Triplet Pair Intermediate Excited States Taffet, Elliot J.; Scholes, Gregory D. The Journal of Physical Chemistry B, Vol. 122, Issue 22 https://doi.org/10.1021/acs.jpcb.8b02504	journal	May 2018
Effects of Molecular Symmetry on the Electronic Transitions in Carotenoids Fiedor, Leszek; Fiedor, Joanna The Journal of Physical Chemistry Letters, Vol. 7, Issue 10 https://doi.org/10.1021/acs.jpclett.6b00637	journal	May 2016
Torsional Dynamics and Intramolecular Charge Transfer in the S ₂ (1 ¹ B _u ⁺ ) Excited State of Peridinin: A Mechanism for Enhanced Mid-Visible Light Harvesting Ghosh, Soumen; Roscioli, Jerome D.; Bishop, Michael M. The Journal of Physical Chemistry Letters, Vol. 7, Issue 18 https://doi.org/10.1021/acs.jpclett.6b01642	journal	September 2016
Carbene–Metal–Amide Bond Deformation, Rather Than Ligand Rotation, Drives Delayed Fluorescence Taffet, Elliot J.; Olivier, Yoann; Lam, Frankie The Journal of Physical Chemistry Letters, Vol. 9, Issue 7 https://doi.org/10.1021/acs.jpclett.8b00503	journal	March 2018
Theoretical analysis of spectra of short polyenes Orlandi, Giorgio.; Zerbetto, Francesco.; Zgierski, Marek Z. Chemical Reviews, Vol. 91, Issue 5 https://doi.org/10.1021/cr00005a012	journal	July 1991
Ultrafast Dynamics of Carotenoid Excited States−From Solution to Natural and Artificial Systems Polívka, Tomáš; Sundström, Villy Chemical Reviews, Vol. 104, Issue 4 https://doi.org/10.1021/cr020674n	journal	April 2004
Single-Reference ab Initio Methods for the Calculation of Excited States of Large Molecules Dreuw, Andreas; Head-Gordon, Martin Chemical Reviews, Vol. 105, Issue 11 https://doi.org/10.1021/cr0505627	journal	November 2005
SHARC: ab Initio Molecular Dynamics with Surface Hopping in the Adiabatic Representation Including Arbitrary Couplings Richter, Martin; Marquetand, Philipp; González-Vázquez, Jesús Journal of Chemical Theory and Computation, Vol. 7, Issue 5 https://doi.org/10.1021/ct1007394	journal	March 2011
Excited States of Butadiene to Chemical Accuracy: Reconciling Theory and Experiment Watson, Mark A.; Chan, Garnet Kin-Lic Journal of Chemical Theory and Computation, Vol. 8, Issue 11 https://doi.org/10.1021/ct300591z	journal	September 2012
Harmonic Models in Cartesian and Internal Coordinates to Simulate the Absorption Spectra of Carotenoids at Finite Temperatures Cerezo, Javier; Zúñiga, José; Requena, Alberto Journal of Chemical Theory and Computation, Vol. 9, Issue 11 https://doi.org/10.1021/ct4005849	journal	October 2013
Performance of the Density Functional Theory/Multireference Configuration Interaction Method on Electronic Excitation of Extended π-Systems Marian, Christel M.; Gilka, Natalie Journal of Chemical Theory and Computation, Vol. 4, Issue 9 https://doi.org/10.1021/ct8001738	journal	July 2008
Fully Integrated Approach to Compute Vibrationally Resolved Optical Spectra: From Small Molecules to Macrosystems Barone, Vincenzo; Bloino, Julien; Biczysko, Malgorzata Journal of Chemical Theory and Computation, Vol. 5, Issue 3 https://doi.org/10.1021/ct8004744	journal	February 2009
S1 and T1 species of .beta.-carotene generated by direct photoexcitation from the all-trans, 9-cis, 13-cis, and 15-cis isomers as revealed by picosecond transient absorption and transient Raman spectroscopies Hashimoto, Hideki; Koyama, Yasushi; Hirata, Yoshinori The Journal of Physical Chemistry, Vol. 95, Issue 8 https://doi.org/10.1021/j100161a022	journal	April 1991
Electronic relaxation in long polyenes Cosgrove, Sarah A.; Guite, Melissa A.; Burnell, Timothy B. The Journal of Physical Chemistry, Vol. 94, Issue 21 https://doi.org/10.1021/j100384a026	journal	October 1990
Chlorophyll Fluorescence and Energy Transfer in the Diatom Nitzschia Closterium. Dutton, Herbert J.; Manning, Winston M.; Duggar, B. M. The Journal of Physical Chemistry, Vol. 47, Issue 4 https://doi.org/10.1021/j150427a002	journal	April 1943
Isolation by high-pressure liquid chromatography of the cis-trans isomers of .beta.-apo-8'-carotenal. Determination of their S0-state configurations by NMR spectroscopy and prediction of their S1- and T1-state configurations by transient Raman spectroscopy Hashimoto, Hideki; Miki, Yousuke; Kuki, Michitaka Journal of the American Chemical Society, Vol. 115, Issue 20 https://doi.org/10.1021/ja00073a042	journal	October 1993
Picosecond time-resolved resonance Raman scattering and absorbance changes from carotenoids in light-harvesting systems of photosynthetic bacterium Chromatium vinosum Hayashi, H.; Kolaczkowski, S. V.; Noguchi, T. Journal of the American Chemical Society, Vol. 112, Issue 12 https://doi.org/10.1021/ja00168a006	journal	June 1990
Symmetry Control of Radiative Decay in Linear Polyenes: Low Barriers for Isomerization in the S ₁ State of Hexadecaheptaene Christensen, Ronald L.; Galinato, Mary Grace I.; Chu, Emily F. Journal of the American Chemical Society, Vol. 129, Issue 6 https://doi.org/10.1021/ja0609607	journal	February 2007
Direct Correlation of Charge Transfer Absorption with Molecular Donor:Acceptor Interfacial Area via Photothermal Deflection Spectroscopy Buchaca-Domingo, Ester; Vandewal, Koen; Fei, Zhuping Journal of the American Chemical Society, Vol. 137, Issue 16 https://doi.org/10.1021/ja512410f	journal	April 2015
Near-Infrared Time-Resolved Study of the S ₁ State Dynamics of the Carotenoid Spheroidene Polívka, Tomáš; Zigmantas, Donatas; Frank, Harry A. The Journal of Physical Chemistry B, Vol. 105, Issue 5 https://doi.org/10.1021/jp002206s	journal	February 2001
Understanding the Energy Transfer Function of LHCII, the Major Light-Harvesting Complex of Green Plants ^† van Amerongen, Herbert; van Grondelle, Rienk The Journal of Physical Chemistry B, Vol. 105, Issue 3 https://doi.org/10.1021/jp0028406	journal	January 2001
Fluorescence Spectroscopy of All- trans -anhydrorhodovibrin and Spirilloxanthin: Detection of the 1B _u ^- Fluorescence Fujii, Ritsuko; Ishikawa, Tatsuya; Koyama, Yasushi The Journal of Physical Chemistry A, Vol. 105, Issue 22 https://doi.org/10.1021/jp010150b	journal	June 2001
Vibrational Relaxation in β-Carotene Probed by Picosecond Stokes and Anti-Stokes Resonance Raman Spectroscopy McCamant, David W.; Kim, Judy E.; Mathies, Richard A. The Journal of Physical Chemistry A, Vol. 106, Issue 25 https://doi.org/10.1021/jp0203595	journal	June 2002
Femtosecond Time-Resolved Stimulated Raman Spectroscopy: Application to the Ultrafast Internal Conversion in β-Carotene ^† McCamant, David W.; Kukura, Philipp; Mathies, Richard A. The Journal of Physical Chemistry A, Vol. 107, Issue 40 https://doi.org/10.1021/jp030147n	journal	October 2003
Pump−Deplete−Probe Spectroscopy and the Puzzle of Carotenoid Dark States Wohlleben, Wendel; Buckup, Tiago; Hashimoto, Hideki The Journal of Physical Chemistry B, Vol. 108, Issue 10 https://doi.org/10.1021/jp036145k	journal	March 2004
Calculation of Solvent Shifts on Electronic g -Tensors with the Conductor-Like Screening Model (COSMO) and Its Self-Consistent Generalization to Real Solvents (Direct COSMO-RS) Sinnecker, Sebastian; Rajendran, Arivazhagan; Klamt, Andreas The Journal of Physical Chemistry A, Vol. 110, Issue 6 https://doi.org/10.1021/jp056016z	journal	February 2006
Pump-Degenerate Four Wave Mixing as a Technique for Analyzing Structural and Electronic Evolution: Multidimensional Time-Resolved Dynamics near a Conical Intersection Hauer, Jürgen; Buckup, Tiago; Motzkus, Marcus The Journal of Physical Chemistry A, Vol. 111, Issue 42 https://doi.org/10.1021/jp073727j	journal	October 2007
On the Nature of the “Dark S*” Excited State of β-Carotene Ostroumov, Evgeny E.; Reus, Marc G. Müller, Michael; Holzwarth, Alfred R. The Journal of Physical Chemistry A, Vol. 115, Issue 16 https://doi.org/10.1021/jp105385c	journal	April 2011
Overcoming Low Orbital Overlap and Triplet Instability Problems in TDDFT Peach, Michael J. G.; Tozer, David J. The Journal of Physical Chemistry A, Vol. 116, Issue 39 https://doi.org/10.1021/jp308662x	journal	September 2012
On the Photophysics of Carotenoids: A Multireference DFT Study of Peridinin Knecht, Stefan; Marian, Christel M.; Kongsted, Jacob The Journal of Physical Chemistry B, Vol. 117, Issue 44 https://doi.org/10.1021/jp4078739	journal	October 2013
Development of a Tunable Femtosecond Stimulated Raman Apparatus and Its Application to β-Carotene Shim, Sangdeok; Mathies, Richard A. The Journal of Physical Chemistry B, Vol. 112, Issue 15 https://doi.org/10.1021/jp710518y	journal	April 2008
Spectroscopic Properties of Spheroidene Analogs Having Different Extents of π-Electron Conjugation Frank, Harry A.; Desamero, Ruel Z. B.; Chynwat, Veeradej The Journal of Physical Chemistry A, Vol. 101, Issue 2 https://doi.org/10.1021/jp962373l	journal	January 1997
Evaluation of Solvent Effects in Isotropic and Anisotropic Dielectrics and in Ionic Solutions with a Unified Integral Equation Method: Theoretical Bases, Computational Implementation, and Numerical Applications Mennucci, B.; Cancès, E.; Tomasi, J. The Journal of Physical Chemistry B, Vol. 101, Issue 49 https://doi.org/10.1021/jp971959k	journal	December 1997
S ₁ and S ₂ States of Apo- and Diapocarotenes Christensen, Ronald L.; Goyette, Michelle; Gallagher, Laurie The Journal of Physical Chemistry A, Vol. 103, Issue 14 https://doi.org/10.1021/jp983946s	journal	April 1999
The 1B _u ⁺ , 1B _u ^- , and 2A _g ^- Energies of Crystalline Lycopene, β-Carotene, and Mini-9-β-carotene as Determined by Resonance-Raman Excitation Profiles: Dependence of the 1B _u ^- State Energy on the Conjugation Length Sashima, Tokutake; Koyama, Yasushi; Yamada, Takashi The Journal of Physical Chemistry B, Vol. 104, Issue 20 https://doi.org/10.1021/jp994185b	journal	May 2000
Organometallic Halide Perovskites: Sharp Optical Absorption Edge and Its Relation to Photovoltaic Performance De Wolf, Stefaan; Holovsky, Jakub; Moon, Soo-Jin The Journal of Physical Chemistry Letters, Vol. 5, Issue 6 https://doi.org/10.1021/jz500279b	journal	March 2014
Low-energy spectrum of iron–sulfur clusters directly from many-particle quantum mechanics Sharma, Sandeep; Sivalingam, Kantharuban; Neese, Frank Nature Chemistry, Vol. 6, Issue 10 https://doi.org/10.1038/nchem.2041	journal	August 2014
A new energy transfer channel from carotenoids to chlorophylls in purple bacteria Feng, Jin; Tseng, Chi-Wei; Chen, Tingwei Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-00120-7	journal	July 2017
Vibronic coupling in the excited-states of carotenoids Miki, Takeshi; Buckup, Tiago; Krause, Marie S. Physical Chemistry Chemical Physics, Vol. 18, Issue 16 https://doi.org/10.1039/C5CP07542D	journal	January 2016
Functionalizing molecular wires: a tunable class of α,ω-diphenyl-μ,ν-dicyano-oligoenes Meisner, Jeffrey S.; Sedbrook, Danielle F.; Krikorian, Markrete Chemical Science, Vol. 3, Issue 4 https://doi.org/10.1039/c2sc00770c	journal	January 2012
Comment on “Reaction field treatment of charge penetration” [J. Chem. Phys. 112, 5558 (2000)] Cancès, Eric; Mennucci, Benedetta The Journal of Chemical Physics, Vol. 114, Issue 10 https://doi.org/10.1063/1.1349091	journal	January 2001
Introduction of n -electron valence states for multireference perturbation theory Angeli, C.; Cimiraglia, R.; Evangelisti, S. The Journal of Chemical Physics, Vol. 114, Issue 23 https://doi.org/10.1063/1.1361246	journal	June 2001
Highly correlated calculations with a polynomial cost algorithm: A study of the density matrix renormalization group Chan, Garnet Kin-Lic; Head-Gordon, Martin The Journal of Chemical Physics, Vol. 116, Issue 11 https://doi.org/10.1063/1.1449459	journal	March 2002
Adiabatic time-dependent density functional methods for excited state properties Furche, Filipp; Ahlrichs, Reinhart The Journal of Chemical Physics, Vol. 117, Issue 16 https://doi.org/10.1063/1.1508368	journal	October 2002
n -electron valence state perturbation theory: A spinless formulation and an efficient implementation of the strongly contracted and of the partially contracted variants Angeli, Celestino; Cimiraglia, Renzo; Malrieu, Jean-Paul The Journal of Chemical Physics, Vol. 117, Issue 20 https://doi.org/10.1063/1.1515317	journal	November 2002
An algorithm for large scale density matrix renormalization group calculations Chan, Garnet Kin-Lic The Journal of Chemical Physics, Vol. 120, Issue 7 https://doi.org/10.1063/1.1638734	journal	February 2004
Effective method to compute Franck-Condon integrals for optical spectra of large molecules in solution Santoro, Fabrizio; Improta, Roberto; Lami, Alessandro The Journal of Chemical Physics, Vol. 126, Issue 8 https://doi.org/10.1063/1.2437197	journal	February 2007
Effective method to compute vibrationally resolved optical spectra of large molecules at finite temperature in the gas phase and in solution Santoro, Fabrizio; Lami, Alessandro; Improta, Roberto The Journal of Chemical Physics, Vol. 126, Issue 18 https://doi.org/10.1063/1.2721539	journal	May 2007
Orbital optimization in the density matrix renormalization group, with applications to polyenes and β-carotene Ghosh, Debashree; Hachmann, Johannes; Yanai, Takeshi The Journal of Chemical Physics, Vol. 128, Issue 14 https://doi.org/10.1063/1.2883976	journal	April 2008
Effective method for the computation of optical spectra of large molecules at finite temperature including the Duschinsky and Herzberg–Teller effect: The Qx band of porphyrin as a case study Santoro, Fabrizio; Lami, Alessandro; Improta, Roberto The Journal of Chemical Physics, Vol. 128, Issue 22 https://doi.org/10.1063/1.2929846	journal	June 2008
Parallel multireference configuration interaction calculations on mini-β-carotenes and β-carotene Kleinschmidt, Martin; Marian, Christel M.; Waletzke, Mirko The Journal of Chemical Physics, Vol. 130, Issue 4 https://doi.org/10.1063/1.3062842	journal	January 2009
Photothermal spectroscopy using optical beam probing: Mirage effect Murphy, J. C.; Aamodt, L. C. Journal of Applied Physics, Vol. 51, Issue 9 https://doi.org/10.1063/1.328350	journal	September 1980
The lowest singlet states of octatetraene revisited Angeli, Celestino; Pastore, Mariachiara The Journal of Chemical Physics, Vol. 134, Issue 18 https://doi.org/10.1063/1.3585607	journal	May 2011
Spin-adapted density matrix renormalization group algorithms for quantum chemistry Sharma, Sandeep; Chan, Garnet Kin-Lic The Journal of Chemical Physics, Vol. 136, Issue 12 https://doi.org/10.1063/1.3695642	journal	March 2012
Electronic excitations in long polyenes revisited Schmidt, Maximilian; Tavan, Paul The Journal of Chemical Physics, Vol. 136, Issue 12 https://doi.org/10.1063/1.3696880	journal	March 2012
Photodynamics of polyenes: The effect of electron correlation on potential surfaces Lasaga, A. C.; Aerni, R. J.; Karplus, M. The Journal of Chemical Physics, Vol. 73, Issue 10 https://doi.org/10.1063/1.439951	journal	November 1980
Absorption and emission of 2,12‐dimethyltridecahexaene Auerbach, Roy A.; Christensen, Ronald L.; Granville, Mark F. The Journal of Chemical Physics, Vol. 74, Issue 1 https://doi.org/10.1063/1.440857	journal	January 1981
The low‐lying electronic excitations in long polyenes: A PPP‐MRD‐CI study Tavan, Paul; Schulten, Klaus The Journal of Chemical Physics, Vol. 85, Issue 11 https://doi.org/10.1063/1.451442	journal	December 1986
Theoretical study of the force field of the lowest singlet electronic states of long polyenes Negri, Fabrizia; Orlandi, Giorgio; Zerbetto, Francesco The Journal of Chemical Physics, Vol. 91, Issue 10 https://doi.org/10.1063/1.457388	journal	November 1989
Density‐functional thermochemistry. I. The effect of the exchange‐only gradient correction Becke, Axel D. The Journal of Chemical Physics, Vol. 96, Issue 3 https://doi.org/10.1063/1.462066	journal	February 1992
Density‐functional thermochemistry. II. The effect of the Perdew–Wang generalized‐gradient correlation correction Becke, Axel D. The Journal of Chemical Physics, Vol. 97, Issue 12 https://doi.org/10.1063/1.463343	journal	December 1992
Continuum solvation models: A new approach to the problem of solute’s charge distribution and cavity boundaries Mennucci, Benedetta; Tomasi, Jacopo The Journal of Chemical Physics, Vol. 106, Issue 12 https://doi.org/10.1063/1.473558	journal	March 1997
The effects of electron correlation on the degree of bond alternation and electronic structure of oligomers of polyacetylene Ho Choi, Cheol; Kertesz, Miklos; Karpfen, Alfred The Journal of Chemical Physics, Vol. 107, Issue 17 https://doi.org/10.1063/1.474914	journal	November 1997
The ab-initio density matrix renormalization group in practice Olivares-Amaya, Roberto; Hu, Weifeng; Nakatani, Naoki The Journal of Chemical Physics, Vol. 142, Issue 3 https://doi.org/10.1063/1.4905329	journal	January 2015
Thermo‐optical spectroscopy: Detection by the ’’mirage effect’’ Boccara, A. C.; Fournier, D.; Badoz, J. Applied Physics Letters, Vol. 36, Issue 2 https://doi.org/10.1063/1.91395	journal	January 1980
Sensitive i n s i t u trace‐gas detection by photothermal deflection spectroscopy Fournier, D.; Boccara, A. C.; Amer, Nabil M. Applied Physics Letters, Vol. 37, Issue 6 https://doi.org/10.1063/1.91970	journal	September 1980
An unusual pathway of excitation energy deactivation in carotenoids: Singlet-to-triplet conversion on an ultrafast timescale in a photosynthetic antenna Gradinaru, C. C.; Kennis, J. T. M.; Papagiannakis, E. Proceedings of the National Academy of Sciences, Vol. 98, Issue 5 https://doi.org/10.1073/pnas.051501298	journal	February 2001
Direct observation of the (forbidden) S1 state in carotenoids Polivka, T.; Herek, J. L.; Zigmantas, D. Proceedings of the National Academy of Sciences, Vol. 96, Issue 9 https://doi.org/10.1073/pnas.96.9.4914	journal	April 1999
Conical intersections and double excitations in time-dependent density functional theory Levine, Benjamin G.; Ko, Chaehyuk; Quenneville, Jason Molecular Physics, Vol. 104, Issue 5-7 https://doi.org/10.1080/00268970500417762	journal	March 2006
Application of unitary group methods to configuration interaction calculations Hegarty, Dermot; Robb, Michael A. Molecular Physics, Vol. 38, Issue 6 https://doi.org/10.1080/00268977900102871	journal	December 1979
The effect of the substrate on photothermal deflection spectroscopy measurements of optical absorption in a-Si:H Rodley, D. R. G.; Jones, D. I.; Stewart, A. D. Philosophical Magazine Letters, Vol. 59, Issue 3 https://doi.org/10.1080/09500838908206336	journal	March 1989
Understanding/unravelling carotenoid excited singlet states Hashimoto, Hideki; Uragami, Chiasa; Yukihira, Nao Journal of The Royal Society Interface, Vol. 15, Issue 141 https://doi.org/10.1098/rsif.2018.0026	journal	April 2018
Inhomogeneous Electron Gas Hohenberg, P.; Kohn, W. Physical Review, Vol. 136, Issue 3B, p. B864-B871 https://doi.org/10.1103/PhysRev.136.B864	journal	November 1964
Self-Consistent Equations Including Exchange and Correlation Effects Kohn, W.; Sham, L. J. Physical Review, Vol. 140, Issue 4A, p. A1133-A1138 https://doi.org/10.1103/PhysRev.140.A1133	journal	November 1965
Electronic excitations in finite and infinite polyenes Tavan, Paul; Schulten, Klaus Physical Review B, Vol. 36, Issue 8 https://doi.org/10.1103/PhysRevB.36.4337	journal	September 1987
Accurate and simple analytic representation of the electron-gas correlation energy Perdew, John P.; Wang, Yue Physical Review B, Vol. 45, Issue 23, p. 13244-13249 https://doi.org/10.1103/PhysRevB.45.13244	journal	June 1992
Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation Perdew, John P.; Chevary, J. A.; Vosko, S. H. Physical Review B, Vol. 46, Issue 11 https://doi.org/10.1103/PhysRevB.46.6671	journal	September 1992
Erratum: Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation Perdew, John P.; Chevary, J. A.; Vosko, S. H. Physical Review B, Vol. 48, Issue 7 https://doi.org/10.1103/PhysRevB.48.4978.2	journal	August 1993
Vibrational relaxation of the 2 A g − excited state in all- trans -β-carotene obtained by femtosecond time-resolved Raman spectroscopy Yoshizawa, M.; Aoki, H.; Hashimoto, H. Physical Review B, Vol. 63, Issue 18 https://doi.org/10.1103/PhysRevB.63.180301	journal	April 2001
Unified explanation for linear and nonlinear optical responses in β -carotene: A sub- 20 − fs degenerate four-wave mixing spectroscopic study Sugisaki, Mitsuru; Yanagi, Kazuhiro; Cogdell, Richard J. Physical Review B, Vol. 75, Issue 15 https://doi.org/10.1103/PhysRevB.75.155110	journal	April 2007
Energy dissipation in the ground-state vibrational manifolds of β -carotene homologues: A sub-20-fs time-resolved transient grating spectroscopic study Fujiwara, Masazumi; Yamauchi, Kensei; Sugisaki, Mitsuru Physical Review B, Vol. 77, Issue 20 https://doi.org/10.1103/PhysRevB.77.205118	journal	May 2008
Photon echo spectroscopy reveals structure-dynamics relationships in carotenoids Christensson, N.; Polivka, T.; Yartsev, A. Physical Review B, Vol. 79, Issue 24 https://doi.org/10.1103/PhysRevB.79.245118	journal	June 2009
Conjugation Length Dependence of Internal Conversion in Carotenoids: Role of the Intermediate State Polli, D.; Cerullo, G.; Lanzani, G. Physical Review Letters, Vol. 93, Issue 16 https://doi.org/10.1103/PhysRevLett.93.163002	journal	October 2004
Singlet Excited States and the Light-Harvesting Function of Carotenoids in Bacterial Photosynthesis Koyama, Yasushi; Kuki, Michitaka; Andersson, Per Ola Photochemistry and Photobiology, Vol. 63, Issue 3 https://doi.org/10.1111/j.1751-1097.1996.tb03021.x	journal	March 1996
Carotenoids in Photosynthesis Frank, Harry A.; Cogdell, Richard J. Photochemistry and Photobiology, Vol. 63, Issue 3 https://doi.org/10.1111/j.1751-1097.1996.tb03022.x	journal	March 1996
Photosynthetic Light Harvesting by Carotenoids: Detection of an Intermediate Excited State Cerullo, G. Science, Vol. 298, Issue 5602 https://doi.org/10.1126/science.1074685	journal	December 2002
Broadband 2D Electronic Spectroscopy Reveals a Carotenoid Dark State in Purple Bacteria Ostroumov, Evgeny E.; Mulvaney, Rachel M.; Cogdell, Richard J. Science, Vol. 340, Issue 6128 https://doi.org/10.1126/science.1230106	journal	April 2013
The density matrix renormalization group for ab initio quantum chemistry Wouters, Sebastian; Van Neck, Dimitri The European Physical Journal D, Vol. 68, Issue 9 https://doi.org/10.1140/epjd/e2014-50500-1	journal	September 2014
Mechanism Activating the 21Ag State in all-trans-β-Carotene Crystal to Resonance Raman Scattering Hashimoto, Hideki; Koyama, Yasushi; Mori, Yuzo Japanese Journal of Applied Physics, Vol. 36, Issue Part 2, No. 7B https://doi.org/10.1143/JJAP.36.L916	journal	July 1997
The Density Matrix Renormalization Group in Quantum Chemistry Chan, Garnet Kin-Lic; Sharma, Sandeep Annual Review of Physical Chemistry, Vol. 62, Issue 1 https://doi.org/10.1146/annurev-physchem-032210-103338	journal	May 2011
Photothermal deflection spectroscopy and detection Jackson, W. B.; Amer, N. M.; Boccara, A. C. Applied Optics, Vol. 20, Issue 8 https://doi.org/10.1364/AO.20.001333	journal	January 1981
Sensitive photothermal deflection technique for measuring absorption in optically thin media Boccara, A. C.; Jackson, Warren; Amer, Nabil M. Optics Letters, Vol. 5, Issue 9 https://doi.org/10.1364/OL.5.000377	journal	January 1980

Similar Records

Carotenoid Nuclear Reorganization and Interplay of Bright and Dark Excited States

Journal Article · Wed Sep 25 00:00:00 EDT 2019 · Journal of Physical Chemistry B · OSTI ID:1571900

Vibronic coupling in the excited-states of carotenoids

Journal Article · Wed Mar 23 00:00:00 EDT 2016 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:1387730

Uncovering dark multichromophoric states in Peridinin–Chlorophyll–Protein

Journal Article · Wed Mar 18 00:00:00 EDT 2020 · Journal of the Royal Society Interface · OSTI ID:1777899

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY

Carotenoid Nuclear Reorganization and Interplay of Bright and Dark Excited States

Citation Formats

References (143)

Similar Records

Related Subjects