The effects of site asymmetry on near-degenerate state-to-state vibronic mixing in flexible bichromophores

Kidwell, Nathanael M.; Nebgen, Benjamin Tyler; Slipchenko, Lyudmila V.; Zwier, Timothy S.

doi:10.1063/1.5107423

The effects of site asymmetry on near-degenerate state-to-state vibronic mixing in flexible bichromophores

Journal Article · Wed Aug 28 00:00:00 EDT 2019 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5107423· OSTI ID:1570631

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Purdue Univ., West Lafayette, IN (United States); College of William and Mary, Williamsburg, VA (United States)
Purdue Univ., West Lafayette, IN (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Purdue Univ., West Lafayette, IN (United States)

Laser-induced fluorescence excitation and dispersed fluorescence spectra of a model flexible bichromophore, 1,1-diphenylethane (DPE), have been recorded under jet-cooled conditions in the gas phase in the region near the first pair of near-degenerate excited states (S₁ and S₂). The S₁ and S₂ origin transitions have been identified at 37 397 and 37 510 cm^–1, a splitting of 113 cm^–1. This splitting is four times smaller than the excitonic splitting calculated by ab initio methods at the EOM-CCSD/cc-pVDZ level of theory (410 cm^–1), which necessarily relies on the Born-Oppenheimer approximation. Dispersed fluorescence spectra provide a state-to-state picture of the vibronic coupling. Furthermore, these results are compared with the results of a multimode vibronic coupling model capable of treating chromophores in asymmetric environments.

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: LDRD; USDOE

Grant/Contract Number:: 89233218CNA000001; FG02-96ER14656

OSTI ID:: 1570631

Alternate ID(s):: OSTI ID: 1567931

Report Number(s):: LA-UR--19-29710

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 8 Vol. 151; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

References (50)

A linear response, coupled-cluster theory for excitation energy Sekino, Hideo; Bartlett, Rodney J. International Journal of Quantum Chemistry, Vol. 26, Issue S18 https://doi.org/10.1002/qua.560260826	journal	March 1984
Consistent assignment of the vibrations of symmetric and asymmetric meta-disubstituted benzenes Kemp, David J.; Tuttle, William D.; Jones, Florence M. S. Journal of Molecular Spectroscopy, Vol. 346 https://doi.org/10.1016/j.jms.2018.02.002	journal	April 2018
Beyond Time-Dependent Density Functional Theory Using Only Single Excitations: Methods for Computational Studies of Excited States in Complex Systems Herbert, John M.; Zhang, Xing; Morrison, Adrian F. Accounts of Chemical Research, Vol. 49, Issue 5 https://doi.org/10.1021/acs.accounts.6b00047	journal	April 2016
Revisiting the Vibrational and Optical Properties of P3HT: A Combined Experimental and Theoretical Study Farouil, Léa; Alary, Fabienne; Bedel-Pereira, Eléna The Journal of Physical Chemistry A, Vol. 122, Issue 32 https://doi.org/10.1021/acs.jpca.8b03814	journal	July 2018
Structural Relaxation of Photoexcited Quaterthiophenes Probed with Vibrational Specificity Zhou, Jiawang; Yu, Wenjian; Bragg, Arthur E. The Journal of Physical Chemistry Letters, Vol. 6, Issue 17 https://doi.org/10.1021/acs.jpclett.5b01472	journal	August 2015
Intramolecular Energy Hopping and Energy Trapping in Polyphenylene Dendrimers with Multiple Peryleneimide Donor Chromophores and a Terryleneimide Acceptor Trap Chromophore Maus, Michael; De, Rina; Lor, Marc Journal of the American Chemical Society, Vol. 123, Issue 31 https://doi.org/10.1021/ja010570e	journal	August 2001
Collective Behavior of Franck−Condon Excited States and Energy Transfer in DNA Double Helices Markovitsi, Dimitra; Onidas, Delphine; Gustavsson, Thomas Journal of the American Chemical Society, Vol. 127, Issue 49 https://doi.org/10.1021/ja054955z	journal	December 2005
Exciton States of Dynamic DNA Double Helices: Alternating dCdG Sequences Emanuele, Emanuela; Zakrzewska, Krystyna; Markovitsi, Dimitra The Journal of Physical Chemistry B, Vol. 109, Issue 33 https://doi.org/10.1021/jp051833k	journal	August 2005
Rotationally Resolved C ₂ Symmetric Conformers of Bis-(4-hydroxyphenyl)methane: Prototypical Examples of Excitonic Coupling in the S ₁ and S ₂ Electronic States Chou, Shin Grace; Rodrigo, Chirantha P.; Müller, Christian W. The Journal of Physical Chemistry A, Vol. 115, Issue 34 https://doi.org/10.1021/jp200804t	journal	September 2011
Twist Angle Plays an Important Role in Photophysical Properties of a Donor–Acceptor-Type Conjugated Polymer: A Combined Ensemble and Single-Molecule Study Habuchi, Satoshi; Fujita, Hiroyuki; Michinobu, Tsuyoshi The Journal of Physical Chemistry B, Vol. 115, Issue 49 https://doi.org/10.1021/jp209405k	journal	December 2011
Exciton Dynamics in Disordered Poly( p -phenylenevinylene). 1. Ultrafast Interconversion and Dynamical Localization Tozer, Oliver Robert; Barford, William The Journal of Physical Chemistry A, Vol. 116, Issue 42 https://doi.org/10.1021/jp307040d	journal	October 2012
Conformational Effects on Excitonic Interactions in a Prototypical H-Bonded Bichromophore: Bis(2-hydroxyphenyl)methane Pillsbury, Nathan R.; Müller, Christian W.; Meerts, W. Leo The Journal of Physical Chemistry A, Vol. 113, Issue 17 https://doi.org/10.1021/jp8098686	journal	April 2009
Coherent Energy Transfer under Incoherent Light Conditions Fassioli, Francesca; Olaya-Castro, Alexandra; Scholes, Gregory D. The Journal of Physical Chemistry Letters, Vol. 3, Issue 21 https://doi.org/10.1021/jz3010317	journal	October 2012
Solvent Effects on Vibronic Coupling in a Flexible Bichromophore: Electronic Localization and Energy Transfer induced by a Single Water Molecule Buchanan, Evan G.; Gord, Joseph R.; Zwier, Timothy S. The Journal of Physical Chemistry Letters, Vol. 4, Issue 10 https://doi.org/10.1021/jz400641p	journal	April 2013
Complexity of excited-state dynamics in DNA Markovitsi, Dimitra; Talbot, Francis; Gustavsson, Thomas Nature, Vol. 441, Issue 7094 https://doi.org/10.1038/nature04903	journal	June 2006
Evidence for wavelike energy transfer through quantum coherence in photosynthetic systems Engel, Gregory S.; Calhoun, Tessa R.; Read, Elizabeth L. Nature, Vol. 446, Issue 7137 https://doi.org/10.1038/nature05678	journal	April 2007
Ion conformation and orientational order in a dicationic ionic liquid crystal studied by solid-state nuclear magnetic resonance spectroscopy Majhi, Debashis; Dvinskikh, Sergey V. Scientific Reports, Vol. 11, Issue 1 https://doi.org/10.1038/s41598-021-85021-y	journal	March 2021
Advances in methods and algorithms in a modern quantum chemistry program package Shao, Yihan; Molnar, Laszlo Fusti; Jung, Yousung Phys. Chem. Chem. Phys., Vol. 8, Issue 27 https://doi.org/10.1039/B517914A	journal	January 2006
Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections Chai, Jeng-Da; Head-Gordon, Martin Physical Chemistry Chemical Physics, Vol. 10, Issue 44 https://doi.org/10.1039/b810189b	journal	January 2008
Excitonic splittings in molecular dimers: why static ab initio calculations cannot match them Ottiger, Philipp; Köppel, Horst; Leutwyler, Samuel Chemical Science, Vol. 6, Issue 11 https://doi.org/10.1039/c5sc02546j	journal	January 2015
S1/S2 exciton splitting in the (2-pyridone)2 dimer Müller, Andreas; Talbot, Francis; Leutwyler, Samuel The Journal of Chemical Physics, Vol. 116, Issue 7 https://doi.org/10.1063/1.1434987	journal	February 2002
Vibronic Coupling. I. Mathematical Treatment for Two Electronic States Fulton, Robert L.; Gouterman, Martin The Journal of Chemical Physics, Vol. 35, Issue 3 https://doi.org/10.1063/1.1701181	journal	September 1961
Time‐of‐Flight Mass Spectrometer with Improved Resolution Wiley, W. C.; McLaren, I. H. Review of Scientific Instruments, Vol. 26, Issue 12 https://doi.org/10.1063/1.1715212	journal	December 1955
Electronic Spectra of Dimers: Derivation of the Fundamental Vibronic Equation Witkowski, Andrzej; Moffitt, William The Journal of Chemical Physics, Vol. 33, Issue 3 https://doi.org/10.1063/1.1731278	journal	September 1960
State-specific studies of internal mixing in a prototypical flexible bichromophore: Diphenylmethane Pillsbury, Nathan R.; Stearns, Jaime A.; Müller, Christian W. The Journal of Chemical Physics, Vol. 129, Issue 11 https://doi.org/10.1063/1.2977730	journal	September 2008
Rotationally resolved studies of S0 and the exciton coupled S1/S2 origin regions of diphenylmethane and the d12 isotopologue Stearns, Jaime A.; Pillsbury, Nathan R.; Douglass, Kevin O. The Journal of Chemical Physics, Vol. 129, Issue 22 https://doi.org/10.1063/1.3028543	journal	December 2008
S1/S2 excitonic splittings and vibronic coupling in the excited state of the jet-cooled 2-aminopyridine dimer Ottiger, Philipp; Leutwyler, Samuel; Köppel, Horst The Journal of Chemical Physics, Vol. 131, Issue 20 https://doi.org/10.1063/1.3266937	journal	November 2009
Conformer-specific vibronic spectroscopy and vibronic coupling in a flexible bichromophore: Bis-(4-hydroxyphenyl)methane Rodrigo, Chirantha P.; Müller, Christian W.; Pillsbury, Nathan R. The Journal of Chemical Physics, Vol. 134, Issue 16 https://doi.org/10.1063/1.3580901	journal	April 2011
The S ₁ / S ₂ exciton interaction in 2-pyridone·6-methyl-2-pyridone: Davydov splitting, vibronic coupling, and vibronic quenching Heid, Cornelia G.; Ottiger, Philipp; Leist, Roman The Journal of Chemical Physics, Vol. 135, Issue 15 https://doi.org/10.1063/1.3652759	journal	October 2011
Phonon-mediated path-interference in electronic energy transfer Hossein-Nejad, Hoda; Olaya-Castro, Alexandra; Scholes, Gregory D. The Journal of Chemical Physics, Vol. 136, Issue 2 https://doi.org/10.1063/1.3675844	journal	January 2012
Vibrational relaxation in jet‐cooled alkyl benzenes. I.Absorption spectra Hopkins, J. B.; Powers, D. E.; Smalley, R. E. The Journal of Chemical Physics, Vol. 72, Issue 9 https://doi.org/10.1063/1.439793	journal	May 1980
Vibrational relaxation in jet‐cooled alkyl benzenes. II. Fluorescence spectra Hopkins, J. B.; Powers, D. E.; Mukamel, S. The Journal of Chemical Physics, Vol. 72, Issue 9 https://doi.org/10.1063/1.439794	journal	May 1980
Excitation energies from the coupled cluster singles and doubles linear response function (CCSDLR). Applications to Be, CH ⁺ , CO, and H ₂ O Koch, Henrik; Jensen, Hans Jo/rgen Aa.; Jo/rgensen, Poul The Journal of Chemical Physics, Vol. 93, Issue 5 https://doi.org/10.1063/1.458815	journal	September 1990
The equation of motion coupled‐cluster method. A systematic biorthogonal approach to molecular excitation energies, transition probabilities, and excited state properties Stanton, John F.; Bartlett, Rodney J. The Journal of Chemical Physics, Vol. 98, Issue 9 https://doi.org/10.1063/1.464746	journal	May 1993
Inhomogeneous dephasing masks coherence lifetimes in ensemble measurements Pelzer, Kenley M.; Griffin, Graham B.; Gray, Stephen K. The Journal of Chemical Physics, Vol. 136, Issue 16 https://doi.org/10.1063/1.4704591	journal	April 2012
Vibrational quenching of excitonic splittings in H-bonded molecular dimers: The electronic Davydov splittings cannot match experiment Ottiger, Philipp; Leutwyler, Samuel; Köppel, Horst The Journal of Chemical Physics, Vol. 136, Issue 17 https://doi.org/10.1063/1.4705119	journal	May 2012
Vibronic coupling in asymmetric bichromophores: Theory and application to diphenylmethane Nebgen, Ben; Emmert, Frank Lee; Slipchenko, Lyudmila V. The Journal of Chemical Physics, Vol. 137, Issue 8 https://doi.org/10.1063/1.4747336	journal	August 2012
Vibrational quenching of excitonic splittings in H-bonded molecular dimers: Adiabatic description and effective mode approximation Kopec, Sabine; Ottiger, Philipp; Leutwyler, Samuel The Journal of Chemical Physics, Vol. 137, Issue 18 https://doi.org/10.1063/1.4763979	journal	November 2012
Excitonic splitting and coherent electronic energy transfer in the gas-phase benzoic acid dimer Ottiger, Philipp; Leutwyler, Samuel The Journal of Chemical Physics, Vol. 137, Issue 20 https://doi.org/10.1063/1.4767400	journal	November 2012
Intermolecular vibrations of jet-cooled (2-pyridone)2: A model for the uracil dimer Müller, Andreas; Talbot, Francis; Leutwyler, Samuel The Journal of Chemical Physics, Vol. 112, Issue 8 https://doi.org/10.1063/1.480524	journal	February 2000
Excitonic splitting and vibronic coupling in 1,2-diphenoxyethane: Conformation-specific effects in the weak coupling limit Buchanan, Evan G.; Walsh, Patrick S.; Plusquellic, David F. The Journal of Chemical Physics, Vol. 138, Issue 20 https://doi.org/10.1063/1.4807300	journal	May 2013
Perspective: Detecting and measuring exciton delocalization in photosynthetic light harvesting Scholes, Gregory D.; Smyth, Cathal The Journal of Chemical Physics, Vol. 140, Issue 11 https://doi.org/10.1063/1.4869329	journal	March 2014
Vibronic coupling in asymmetric bichromophores: Experimental investigation of diphenylmethane- d ₅ Pillsbury, Nathan R.; Kidwell, Nathanael M.; Nebgen, Benjamin The Journal of Chemical Physics, Vol. 141, Issue 6 https://doi.org/10.1063/1.4892344	journal	August 2014
Vibronic coupling in asymmetric bichromophores: Theory and application to diphenylmethane- d ₅ Nebgen, Benjamin; Slipchenko, Lyudmila V. The Journal of Chemical Physics, Vol. 141, Issue 13 https://doi.org/10.1063/1.4896561	journal	October 2014
Direct evidence of quantum transport in photosynthetic light-harvesting complexes Panitchayangkoon, G.; Voronine, D. V.; Abramavicius, D. Proceedings of the National Academy of Sciences, Vol. 108, Issue 52 https://doi.org/10.1073/pnas.1105234108	journal	December 2011
Elucidation of near-resonance vibronic coherence lifetimes by nonadiabatic electronic-vibrational state character mixing Yeh, Shu-Hao; Hoehn, Ross D.; Allodi, Marco A. Proceedings of the National Academy of Sciences, Vol. 116, Issue 37 https://doi.org/10.1073/pnas.1701390115	journal	August 2018
Localization of electronic and vibrational energy in the jet-cooled m -cyanophenol/ o -cyanophenol dimer: laser induced fluorescence and fluorescence-dip IR spectra Le Barbu-Debus, K.; Broquier, M.; Lahmani, F. Molecular Physics, Vol. 103, Issue 11-12 https://doi.org/10.1080/00268970500077608	journal	June 2005
Coherence Dynamics in Photosynthesis: Protein Protection of Excitonic Coherence Lee, H.; Cheng, Y. -C.; Fleming, G. R. Science, Vol. 316, Issue 5830 https://doi.org/10.1126/science.1142188	journal	June 2007
L ONG -R ANGE R ESONANCE E NERGY T RANSFER IN M OLECULAR S YSTEMS Scholes, Gregory D. Annual Review of Physical Chemistry, Vol. 54, Issue 1 https://doi.org/10.1146/annurev.physchem.54.011002.103746	journal	October 2003
Equation-of-Motion Coupled-Cluster Methods for Open-Shell and Electronically Excited Species: The Hitchhiker's Guide to Fock Space Krylov, Anna I. Annual Review of Physical Chemistry, Vol. 59, Issue 1 https://doi.org/10.1146/annurev.physchem.59.032607.093602	journal	May 2008

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