Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

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

Abstract

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.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]
+ Show Author Affiliations
  1. Purdue Univ., West Lafayette, IN (United States); College of William and Mary, Williamsburg, VA (United States)
  2. Purdue Univ., West Lafayette, IN (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Purdue Univ., West Lafayette, IN (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1570631
Alternate Identifier(s):
OSTI ID: 1567931
Report Number(s):
LA-UR-19-29710
Journal ID: ISSN 0021-9606; TRN: US2001237
Grant/Contract Number:  
89233218CNA000001; FG02-96ER14656
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 8; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Inorganic and Physical Chemistry

Citation Formats

Kidwell, Nathanael M., Nebgen, Benjamin Tyler, Slipchenko, Lyudmila V., and Zwier, Timothy S. The effects of site asymmetry on near-degenerate state-to-state vibronic mixing in flexible bichromophores. United States: N. p., 2019. Web. doi:10.1063/1.5107423.
Copy to clipboard
Kidwell, Nathanael M., Nebgen, Benjamin Tyler, Slipchenko, Lyudmila V., & Zwier, Timothy S. The effects of site asymmetry on near-degenerate state-to-state vibronic mixing in flexible bichromophores. United States. https://doi.org/10.1063/1.5107423
Copy to clipboard
Kidwell, Nathanael M., Nebgen, Benjamin Tyler, Slipchenko, Lyudmila V., and Zwier, Timothy S. Wed . "The effects of site asymmetry on near-degenerate state-to-state vibronic mixing in flexible bichromophores". United States. https://doi.org/10.1063/1.5107423. https://www.osti.gov/servlets/purl/1570631.
Copy to clipboard
@article{osti_1570631,
title = {The effects of site asymmetry on near-degenerate state-to-state vibronic mixing in flexible bichromophores},
author = {Kidwell, Nathanael M. and Nebgen, Benjamin Tyler and Slipchenko, Lyudmila V. and Zwier, Timothy S.},
abstractNote = {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.},
doi = {10.1063/1.5107423},
journal = {Journal of Chemical Physics},
number = 8,
volume = 151,
place = {United States},
year = {Wed Aug 28 00:00:00 EDT 2019},
month = {Wed Aug 28 00:00:00 EDT 2019}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1063/1.5107423
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Perspective: Detecting and measuring exciton delocalization in photosynthetic light harvesting
journal, March 2014

  • Scholes, Gregory D.; Smyth, Cathal
  • The Journal of Chemical Physics, Vol. 140, Issue 11
  • DOI: 10.1063/1.4869329

Vibrational quenching of excitonic splittings in H-bonded molecular dimers: Adiabatic description and effective mode approximation
journal, November 2012

  • Kopec, Sabine; Ottiger, Philipp; Leutwyler, Samuel
  • The Journal of Chemical Physics, Vol. 137, Issue 18
  • DOI: 10.1063/1.4763979

State-specific studies of internal mixing in a prototypical flexible bichromophore: Diphenylmethane
journal, September 2008

  • Pillsbury, Nathan R.; Stearns, Jaime A.; Müller, Christian W.
  • The Journal of Chemical Physics, Vol. 129, Issue 11
  • DOI: 10.1063/1.2977730

Vibronic coupling in asymmetric bichromophores: Experimental investigation of diphenylmethane- d 5
journal, August 2014

  • Pillsbury, Nathan R.; Kidwell, Nathanael M.; Nebgen, Benjamin
  • The Journal of Chemical Physics, Vol. 141, Issue 6
  • DOI: 10.1063/1.4892344

A linear response, coupled-cluster theory for excitation energy
journal, March 1984

  • Sekino, Hideo; Bartlett, Rodney J.
  • International Journal of Quantum Chemistry, Vol. 26, Issue S18
  • DOI: 10.1002/qua.560260826

Exciton States of Dynamic DNA Double Helices:  Alternating dCdG Sequences
journal, August 2005

  • Emanuele, Emanuela; Zakrzewska, Krystyna; Markovitsi, Dimitra
  • The Journal of Physical Chemistry B, Vol. 109, Issue 33
  • DOI: 10.1021/jp051833k

Excitation energies from the coupled cluster singles and doubles linear response function (CCSDLR). Applications to Be, CH + , CO, and H 2 O
journal, September 1990

  • Koch, Henrik; Jensen, Hans Jo/rgen Aa.; Jo/rgensen, Poul
  • The Journal of Chemical Physics, Vol. 93, Issue 5
  • DOI: 10.1063/1.458815

Coherent Energy Transfer under Incoherent Light Conditions
journal, October 2012

  • Fassioli, Francesca; Olaya-Castro, Alexandra; Scholes, Gregory D.
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 21
  • DOI: 10.1021/jz3010317

Consistent assignment of the vibrations of symmetric and asymmetric meta-disubstituted benzenes
journal, April 2018

  • Kemp, David J.; Tuttle, William D.; Jones, Florence M. S.
  • Journal of Molecular Spectroscopy, Vol. 346
  • DOI: 10.1016/j.jms.2018.02.002

Vibronic Coupling. I. Mathematical Treatment for Two Electronic States
journal, September 1961

  • Fulton, Robert L.; Gouterman, Martin
  • The Journal of Chemical Physics, Vol. 35, Issue 3
  • DOI: 10.1063/1.1701181

L ONG -R ANGE R ESONANCE E NERGY T RANSFER IN M OLECULAR S YSTEMS
journal, October 2003

Advances in methods and algorithms in a modern quantum chemistry program package
journal, January 2006

  • Shao, Yihan; Molnar, Laszlo Fusti; Jung, Yousung
  • Phys. Chem. Chem. Phys., Vol. 8, Issue 27
  • DOI: 10.1039/B517914A

Revisiting the Vibrational and Optical Properties of P3HT: A Combined Experimental and Theoretical Study
journal, July 2018

  • Farouil, Léa; Alary, Fabienne; Bedel-Pereira, Eléna
  • The Journal of Physical Chemistry A, Vol. 122, Issue 32
  • DOI: 10.1021/acs.jpca.8b03814

Rotationally resolved studies of S0 and the exciton coupled S1/S2 origin regions of diphenylmethane and the d12 isotopologue
journal, December 2008

  • Stearns, Jaime A.; Pillsbury, Nathan R.; Douglass, Kevin O.
  • The Journal of Chemical Physics, Vol. 129, Issue 22
  • DOI: 10.1063/1.3028543

Exciton Dynamics in Disordered Poly( p -phenylenevinylene). 1. Ultrafast Interconversion and Dynamical Localization
journal, October 2012

  • Tozer, Oliver Robert; Barford, William
  • The Journal of Physical Chemistry A, Vol. 116, Issue 42
  • DOI: 10.1021/jp307040d

Evidence for wavelike energy transfer through quantum coherence in photosynthetic systems
journal, April 2007

  • Engel, Gregory S.; Calhoun, Tessa R.; Read, Elizabeth L.
  • Nature, Vol. 446, Issue 7137
  • DOI: 10.1038/nature05678

Complexity of excited-state dynamics in DNA
journal, June 2006

  • Markovitsi, Dimitra; Talbot, Francis; Gustavsson, Thomas
  • Nature, Vol. 441, Issue 7094
  • DOI: 10.1038/nature04903

Coherence Dynamics in Photosynthesis: Protein Protection of Excitonic Coherence
journal, June 2007

The S 1 / S 2 exciton interaction in 2-pyridone·6-methyl-2-pyridone: Davydov splitting, vibronic coupling, and vibronic quenching
journal, October 2011

  • Heid, Cornelia G.; Ottiger, Philipp; Leist, Roman
  • The Journal of Chemical Physics, Vol. 135, Issue 15
  • DOI: 10.1063/1.3652759

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
journal, September 2011

  • Chou, Shin Grace; Rodrigo, Chirantha P.; Müller, Christian W.
  • The Journal of Physical Chemistry A, Vol. 115, Issue 34
  • DOI: 10.1021/jp200804t

Time‐of‐Flight Mass Spectrometer with Improved Resolution
journal, December 1955

  • Wiley, W. C.; McLaren, I. H.
  • Review of Scientific Instruments, Vol. 26, Issue 12
  • DOI: 10.1063/1.1715212

Intramolecular Energy Hopping and Energy Trapping in Polyphenylene Dendrimers with Multiple Peryleneimide Donor Chromophores and a Terryleneimide Acceptor Trap Chromophore
journal, August 2001

  • Maus, Michael; De, Rina; Lor, Marc
  • Journal of the American Chemical Society, Vol. 123, Issue 31
  • DOI: 10.1021/ja010570e

Direct evidence of quantum transport in photosynthetic light-harvesting complexes
journal, December 2011

  • Panitchayangkoon, G.; Voronine, D. V.; Abramavicius, D.
  • Proceedings of the National Academy of Sciences, Vol. 108, Issue 52
  • DOI: 10.1073/pnas.1105234108

Electronic Spectra of Dimers: Derivation of the Fundamental Vibronic Equation
journal, September 1960

  • Witkowski, Andrzej; Moffitt, William
  • The Journal of Chemical Physics, Vol. 33, Issue 3
  • DOI: 10.1063/1.1731278

S1/S2 excitonic splittings and vibronic coupling in the excited state of the jet-cooled 2-aminopyridine dimer
journal, November 2009

  • Ottiger, Philipp; Leutwyler, Samuel; Köppel, Horst
  • The Journal of Chemical Physics, Vol. 131, Issue 20
  • DOI: 10.1063/1.3266937

S1/S2 exciton splitting in the (2-pyridone)2 dimer
journal, February 2002

  • Müller, Andreas; Talbot, Francis; Leutwyler, Samuel
  • The Journal of Chemical Physics, Vol. 116, Issue 7
  • DOI: 10.1063/1.1434987

Excitonic splitting and coherent electronic energy transfer in the gas-phase benzoic acid dimer
journal, November 2012

  • Ottiger, Philipp; Leutwyler, Samuel
  • The Journal of Chemical Physics, Vol. 137, Issue 20
  • DOI: 10.1063/1.4767400

Vibronic coupling in asymmetric bichromophores: Theory and application to diphenylmethane
journal, August 2012

  • Nebgen, Ben; Emmert, Frank Lee; Slipchenko, Lyudmila V.
  • The Journal of Chemical Physics, Vol. 137, Issue 8
  • DOI: 10.1063/1.4747336

Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections
journal, January 2008

  • Chai, Jeng-Da; Head-Gordon, Martin
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 44
  • DOI: 10.1039/b810189b

Structural Relaxation of Photoexcited Quaterthiophenes Probed with Vibrational Specificity
journal, August 2015

  • Zhou, Jiawang; Yu, Wenjian; Bragg, Arthur E.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 17
  • DOI: 10.1021/acs.jpclett.5b01472

Intermolecular vibrations of jet-cooled (2-pyridone)2: A model for the uracil dimer
journal, February 2000

  • Müller, Andreas; Talbot, Francis; Leutwyler, Samuel
  • The Journal of Chemical Physics, Vol. 112, Issue 8
  • DOI: 10.1063/1.480524

Conformer-specific vibronic spectroscopy and vibronic coupling in a flexible bichromophore: Bis-(4-hydroxyphenyl)methane
journal, April 2011

  • Rodrigo, Chirantha P.; Müller, Christian W.; Pillsbury, Nathan R.
  • The Journal of Chemical Physics, Vol. 134, Issue 16
  • DOI: 10.1063/1.3580901

Phonon-mediated path-interference in electronic energy transfer
journal, January 2012

  • Hossein-Nejad, Hoda; Olaya-Castro, Alexandra; Scholes, Gregory D.
  • The Journal of Chemical Physics, Vol. 136, Issue 2
  • DOI: 10.1063/1.3675844

Excitonic splitting and vibronic coupling in 1,2-diphenoxyethane: Conformation-specific effects in the weak coupling limit
journal, May 2013

  • Buchanan, Evan G.; Walsh, Patrick S.; Plusquellic, David F.
  • The Journal of Chemical Physics, Vol. 138, Issue 20
  • DOI: 10.1063/1.4807300

Twist Angle Plays an Important Role in Photophysical Properties of a Donor–Acceptor-Type Conjugated Polymer: A Combined Ensemble and Single-Molecule Study
journal, December 2011

  • Habuchi, Satoshi; Fujita, Hiroyuki; Michinobu, Tsuyoshi
  • The Journal of Physical Chemistry B, Vol. 115, Issue 49
  • DOI: 10.1021/jp209405k

Vibronic coupling in asymmetric bichromophores: Theory and application to diphenylmethane- d 5
journal, October 2014

  • Nebgen, Benjamin; Slipchenko, Lyudmila V.
  • The Journal of Chemical Physics, Vol. 141, Issue 13
  • DOI: 10.1063/1.4896561

Collective Behavior of Franck−Condon Excited States and Energy Transfer in DNA Double Helices
journal, December 2005

  • Markovitsi, Dimitra; Onidas, Delphine; Gustavsson, Thomas
  • Journal of the American Chemical Society, Vol. 127, Issue 49
  • DOI: 10.1021/ja054955z

Vibrational relaxation in jet‐cooled alkyl benzenes. II. Fluorescence spectra
journal, May 1980

  • Hopkins, J. B.; Powers, D. E.; Mukamel, S.
  • The Journal of Chemical Physics, Vol. 72, Issue 9
  • DOI: 10.1063/1.439794

Vibrational relaxation in jet‐cooled alkyl benzenes. I.Absorption spectra
journal, May 1980

  • Hopkins, J. B.; Powers, D. E.; Smalley, R. E.
  • The Journal of Chemical Physics, Vol. 72, Issue 9
  • DOI: 10.1063/1.439793

Solvent Effects on Vibronic Coupling in a Flexible Bichromophore: Electronic Localization and Energy Transfer induced by a Single Water Molecule
journal, April 2013

  • Buchanan, Evan G.; Gord, Joseph R.; Zwier, Timothy S.
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 10
  • DOI: 10.1021/jz400641p

Inhomogeneous dephasing masks coherence lifetimes in ensemble measurements
journal, April 2012

  • Pelzer, Kenley M.; Griffin, Graham B.; Gray, Stephen K.
  • The Journal of Chemical Physics, Vol. 136, Issue 16
  • DOI: 10.1063/1.4704591

Beyond Time-Dependent Density Functional Theory Using Only Single Excitations: Methods for Computational Studies of Excited States in Complex Systems
journal, April 2016

Elucidation of near-resonance vibronic coherence lifetimes by nonadiabatic electronic-vibrational state character mixing
journal, August 2018

  • Yeh, Shu-Hao; Hoehn, Ross D.; Allodi, Marco A.
  • Proceedings of the National Academy of Sciences, Vol. 116, Issue 37
  • DOI: 10.1073/pnas.1701390115

Excitonic splittings in molecular dimers: why static ab initio calculations cannot match them
journal, January 2015

  • Ottiger, Philipp; Köppel, Horst; Leutwyler, Samuel
  • Chemical Science, Vol. 6, Issue 11
  • DOI: 10.1039/c5sc02546j

Conformational Effects on Excitonic Interactions in a Prototypical H-Bonded Bichromophore: Bis(2-hydroxyphenyl)methane
journal, April 2009

  • Pillsbury, Nathan R.; Müller, Christian W.; Meerts, W. Leo
  • The Journal of Physical Chemistry A, Vol. 113, Issue 17
  • DOI: 10.1021/jp8098686

Vibrational quenching of excitonic splittings in H-bonded molecular dimers: The electronic Davydov splittings cannot match experiment
journal, May 2012

  • Ottiger, Philipp; Leutwyler, Samuel; Köppel, Horst
  • The Journal of Chemical Physics, Vol. 136, Issue 17
  • DOI: 10.1063/1.4705119
    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: