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

Title: Resonance Raman Spectroscopy of the T1 Triplet Excited State of Oligothiophenes

Abstract

The characterization of triplet excited states is essential for research on organic photovoltaics and singlet fission. We report resonance Raman spectra of two triplet oligothiophenes with n-alkyl substituents, a tetramer and hexamer. The spectra of the triplets are more complex than the ground state, and we find that density functional theory calculations are a useful starting point for characterizing the bands. The spectra of triplet tetrathiophene and hexathiophene differ significantly from one another. This observation is consistent with a T1 excitation that is delocalized over at least five rings in long oligomers. Bands in the 500–800 cm–1 region are greatly diminished for an aggregated sample of hexathiophene, likely caused by fast electronic dephasing. These experiments highlight the potential of resonance Raman spectroscopy to unequivocally detect and characterize triplets in thiophene materials. Furthermore, the vibrational spectra can also serve as rigorous standards for evaluating computational methods for excited-state molecules.

Authors:
 [1];  [1];  [1];  [2];  [3];  [2];  [1]
+ Show Author Affiliations
  1. Univ. of California at San Diego, La Jolla, CA (United States)
  2. Univ. of Texas, Austin, TX (United States)
  3. Rice Univ., Houston, TX (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Understanding Charge Separation and Transfer at Interfaces in Energy Materials (CST)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1370055
Grant/Contract Number:  
SC0001091; CHE-1057198; P200A120223; CHE-0847763; CHE-1362381
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 6; Journal Issue: 18; Related Information: CST partners with University of Texas at Austin (lead); Sandia National Laboratories; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Polythiophene; hexathiophene; sexithiophene; tetrathiophene; quaterthiophene; vibration; aggregate

Citation Formats

Wang, Chen, Angelella, Maria, Doyle, Samantha J., Lytwak, Lauren A., Rossky, Peter J., Holliday, Bradley J., and Tauber, Michael J. Resonance Raman Spectroscopy of the T1 Triplet Excited State of Oligothiophenes. United States: N. p., 2015. Web. doi:10.1021/acs.jpclett.5b01410.
Copy to clipboard
Wang, Chen, Angelella, Maria, Doyle, Samantha J., Lytwak, Lauren A., Rossky, Peter J., Holliday, Bradley J., & Tauber, Michael J. Resonance Raman Spectroscopy of the T1 Triplet Excited State of Oligothiophenes. United States. https://doi.org/10.1021/acs.jpclett.5b01410
Copy to clipboard
Wang, Chen, Angelella, Maria, Doyle, Samantha J., Lytwak, Lauren A., Rossky, Peter J., Holliday, Bradley J., and Tauber, Michael J. Wed . "Resonance Raman Spectroscopy of the T1 Triplet Excited State of Oligothiophenes". United States. https://doi.org/10.1021/acs.jpclett.5b01410. https://www.osti.gov/servlets/purl/1370055.
Copy to clipboard
@article{osti_1370055,
title = {Resonance Raman Spectroscopy of the T1 Triplet Excited State of Oligothiophenes},
author = {Wang, Chen and Angelella, Maria and Doyle, Samantha J. and Lytwak, Lauren A. and Rossky, Peter J. and Holliday, Bradley J. and Tauber, Michael J.},
abstractNote = {The characterization of triplet excited states is essential for research on organic photovoltaics and singlet fission. We report resonance Raman spectra of two triplet oligothiophenes with n-alkyl substituents, a tetramer and hexamer. The spectra of the triplets are more complex than the ground state, and we find that density functional theory calculations are a useful starting point for characterizing the bands. The spectra of triplet tetrathiophene and hexathiophene differ significantly from one another. This observation is consistent with a T1 excitation that is delocalized over at least five rings in long oligomers. Bands in the 500–800 cm–1 region are greatly diminished for an aggregated sample of hexathiophene, likely caused by fast electronic dephasing. These experiments highlight the potential of resonance Raman spectroscopy to unequivocally detect and characterize triplets in thiophene materials. Furthermore, the vibrational spectra can also serve as rigorous standards for evaluating computational methods for excited-state molecules.},
doi = {10.1021/acs.jpclett.5b01410},
journal = {Journal of Physical Chemistry Letters},
number = 18,
volume = 6,
place = {United States},
year = {Wed Aug 19 00:00:00 EDT 2015},
month = {Wed Aug 19 00:00:00 EDT 2015}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpclett.5b01410
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 15 works
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:

Electroluminescence in conjugated polymers
journal, January 1999

  • Friend, R. H.; Gymer, R. W.; Holmes, A. B.
  • Nature, Vol. 397, Issue 6715
  • DOI: 10.1038/16393

Fluorescence and Phosphorescence in Organic Materials
journal, May 2002

Triplet states in organic semiconductors
journal, November 2009

An Organic Electronics Primer
journal, May 2005

  • Malliaras, George; Friend, Richard
  • Physics Today, Vol. 58, Issue 5
  • DOI: 10.1063/1.1995748

Highly efficient phosphorescent emission from organic electroluminescent devices
journal, September 1998

  • Baldo, M. A.; O'Brien, D. F.; You, Y.
  • Nature, Vol. 395, Issue 6698, p. 151-154
  • DOI: 10.1038/25954

Radical ion pair mediated triplet formation in polymer–fullerene blend films
journal, January 2006

  • Ohkita, Hideo; Cook, Steffan; Astuti, Yeni
  • Chem. Commun., Issue 37
  • DOI: 10.1039/b608832e

Charge Recombination in Organic Photovoltaic Devices with High Open-Circuit Voltages
journal, October 2008

  • Westenhoff, Sebastian; Howard, Ian A.; Hodgkiss, Justin M.
  • Journal of the American Chemical Society, Vol. 130, Issue 41
  • DOI: 10.1021/ja803054g

The role of spin in the kinetic control of recombination in organic photovoltaics
journal, August 2013

  • Rao, Akshay; Chow, Philip C. Y.; Gélinas, Simon
  • Nature, Vol. 500, Issue 7463
  • DOI: 10.1038/nature12339

Bimolecular Recombination in Organic Photovoltaics
journal, April 2014

Efficient Organic Heterojunction Photovoltaic Cells Based on Triplet Materials
journal, December 2005

Triplet vs Singlet Energy Transfer in Organic Semiconductors: The Tortoise and the Hare
journal, August 2012

  • Yost, Shane R.; Hontz, Eric; Yeganeh, Sina
  • The Journal of Physical Chemistry C, Vol. 116, Issue 33
  • DOI: 10.1021/jp304433t

Singlet Fission
journal, November 2010

  • Smith, Millicent B.; Michl, Josef
  • Chemical Reviews, Vol. 110, Issue 11
  • DOI: 10.1021/cr1002613

Solar conversion efficiency of photovoltaic and photoelectrolysis cells with carrier multiplication absorbers
journal, October 2006

  • Hanna, M. C.; Nozik, A. J.
  • Journal of Applied Physics, Vol. 100, Issue 7
  • DOI: 10.1063/1.2356795

Thermodynamic Limit of Exciton Fission Solar Cell Efficiency
journal, September 2012

  • Tayebjee, Murad J. Y.; Gray-Weale, Angus A.; Schmidt, Timothy W.
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 19
  • DOI: 10.1021/jz301069u

Spatial extent of the singlet and triplet excitons in transition metal‐containing poly‐ynes
journal, September 1996

  • Beljonne, D.; Wittmann, H. F.; Köhler, A.
  • The Journal of Chemical Physics, Vol. 105, Issue 9
  • DOI: 10.1063/1.472207

Spatial Extension of Excitons in Triphenylene-Based Polymers Given by Range-Separated Functionals
journal, November 2013

  • Kociper, Birgit; Niehaus, Thomas A.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 49
  • DOI: 10.1021/jp407828h

Localization of Electronic Excitations in Conjugated Polymers Studied by DFT
journal, February 2011

  • Nayyar, Iffat H.; Batista, Enrique R.; Tretiak, Sergei
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 6
  • DOI: 10.1021/jz101740w

The Singlet–Triplet Exchange Energy in Conjugated Polymers
journal, January 2004

Excitons in nanoscale systems
journal, September 2006

  • Scholes, Gregory D.; Rumbles, Garry
  • Nature Materials, Vol. 5, Issue 9
  • DOI: 10.1038/nmat1710

Triplet State Absorption in Carbon Nanotubes:  A TD−DFT Study
journal, August 2007

Comprehensive Evaluation of the Absorption, Photophysical, Energy Transfer, Structural, and Theoretical Properties of α-Oligothiophenes with One to Seven Rings
journal, January 1996

  • Becker, Ralph S.; Seixas de Melo, J.; Maçanita, António L.
  • The Journal of Physical Chemistry, Vol. 100, Issue 48
  • DOI: 10.1021/jp960852e

Influence of Chain Length and Derivatization on the Lowest Singlet and Triplet States and Intersystem Crossing in Oligothiophenes
journal, January 1996

  • Beljonne, D.; Cornil, J.; Friend, R. H.
  • Journal of the American Chemical Society, Vol. 118, Issue 27
  • DOI: 10.1021/ja9531135

Pulsed EPR Spectroscopy of the Photoexcited Triplet States of Thiophene Oligomers in Frozen Solution
journal, January 1996

  • Bennati, Marina; Grupp, Arthur; Mehring, Michael
  • The Journal of Physical Chemistry, Vol. 100, Issue 8
  • DOI: 10.1021/jp9522728

Throwing light on dark states of α-oligothiophenes of chain lengths 2 to 6: radical anion photoelectron spectroscopy and excited-state theory
journal, January 2011

  • Siegert, S.; Vogeler, F.; Marian, C. M.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 21
  • DOI: 10.1039/c0cp02712j

Energy Levels of Oligothiophenes in the Higher Excited Triplet States
journal, January 2007

  • Oseki, Yosuke; Fujitsuka, Mamoru; Sakamoto, Masanori
  • The Journal of Physical Chemistry C, Vol. 111, Issue 2
  • DOI: 10.1021/jp065714w

The effect of conjugation length on triplet energies, electron delocalization and electron–electron correlation in soluble polythiophenes
journal, November 2001

  • Monkman, A. P.; Burrows, H. D.; Hamblett, I.
  • The Journal of Chemical Physics, Vol. 115, Issue 19
  • DOI: 10.1063/1.1412868

Singlet and triplet energies of α-oligothiophenes: A spectroscopic, theoretical, and photoacoustic study: Extrapolation to polythiophene
journal, September 1999

  • de Melo, J. Seixas; Silva, Luı́s M.; Arnaut, Luı́s G.
  • The Journal of Chemical Physics, Vol. 111, Issue 12
  • DOI: 10.1063/1.479825

Optical detection of the lowest triplet excited state of oligothiophenes and anthryloligothiophenes
journal, September 1996

Size dependence of triplet and singlet states of α-oligothiophenes
journal, January 1999

  • Rentsch, S.; Yang, J. P.; Paa, W.
  • Physical Chemistry Chemical Physics, Vol. 1, Issue 8
  • DOI: 10.1039/a808617f

Phosphorescence and Triplet State Energies of Oligothiophenes
journal, March 2005

  • Wasserberg, Dorothee; Marsal, Philippe; Meskers, Stefan C. J.
  • The Journal of Physical Chemistry B, Vol. 109, Issue 10
  • DOI: 10.1021/jp0457085

Theoretical Study of Singlet and Triplet Excitation Energies in Oligothiophenes
journal, April 2005

  • Fabiano, E.; Sala, F. Della; Cingolani, R.
  • The Journal of Physical Chemistry A, Vol. 109, Issue 13
  • DOI: 10.1021/jp044974f

Optically detected magnetic resonance (ODMR) studies of conducting polymers: an overview
journal, August 1992

Triplet polaronic excitons in conducting polymers: an X-band optically detected magnetic resonance (ODMR) study
journal, August 1992

Excitation dynamics in single molecular crystals of α-hexathiophene from femtoseconds to milliseconds
journal, April 2001

Zero‐field‐splitting and π‐electron spin densities in the lowest excited triplet state of oligothiophenes
journal, September 1996

  • Bennati, M.; Németh, K.; Surján, P. R.
  • The Journal of Chemical Physics, Vol. 105, Issue 11
  • DOI: 10.1063/1.472296

Near-IR Femtosecond Transient Absorption Spectroscopy of Ultrafast Polaron and Triplet Exciton Formation in Polythiophene Films with Different Regioregularities
journal, November 2009

  • Guo, Jiamo; Ohkita, Hideo; Benten, Hiroaki
  • Journal of the American Chemical Society, Vol. 131, Issue 46
  • DOI: 10.1021/ja906621a

Activated Singlet Exciton Fission in a Semiconducting Polymer
journal, August 2013

  • Musser, Andrew J.; Al-Hashimi, Mohammed; Maiuri, Margherita
  • Journal of the American Chemical Society, Vol. 135, Issue 34
  • DOI: 10.1021/ja405427j

High Yield Ultrafast Intramolecular Singlet Exciton Fission in a Quinoidal Bithiophene
journal, April 2015

  • Varnavski, Oleg; Abeyasinghe, Neranga; Aragó, Juan
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 8
  • DOI: 10.1021/acs.jpclett.5b00198

Electronic Absorption and Vibrational Spectroscopies of Conjugated Conducting Polymers
journal, January 1996

  • Furukawa, Yukio
  • The Journal of Physical Chemistry, Vol. 100, Issue 39
  • DOI: 10.1021/jp960608n

Dynamics of polythiophene with defects
journal, November 1991

  • Poussigue, G.; Benoit, C.; Sauvajol, J. -L
  • Journal of Physics: Condensed Matter, Vol. 3, Issue 45
  • DOI: 10.1088/0953-8984/3/45/005

Vibrational Studies of a Series of .alpha.-Oligothiophenes as Model Systems of Polythiophene
journal, July 1995

  • Louarn, G.; Buisson, J. P.; Lefrant, S.
  • The Journal of Physical Chemistry, Vol. 99, Issue 29
  • DOI: 10.1021/j100029a016

The intramolecular vibrations of prototypical polythiophenes
journal, June 1996

  • Degli Esposti, Alessandra; Moze, O.; Taliani, C.
  • The Journal of Chemical Physics, Vol. 104, Issue 24
  • DOI: 10.1063/1.471757

The polarized infrared and Raman spectra of α-T6 single crystal: An experimental and theoretical study
journal, April 2000

  • Degli Esposti, Alessandra; Fanti, Marianna; Muccini, Michele
  • The Journal of Chemical Physics, Vol. 112, Issue 13
  • DOI: 10.1063/1.481182

Raman Spectroscopy of Short-Lived Terthiophene Radical Cations Generated by Photochemical and Chemical Oxidation
journal, June 2006

  • Clarke, Tracey M.; Gordon, Keith C.; Chan, Wing Sum
  • ChemPhysChem, Vol. 7, Issue 6
  • DOI: 10.1002/cphc.200500680

The Frontiers of Quinoidal Stability in Long Oligothiophenes: Raman Spectra of Dicationic Polaron Pairs
journal, October 2011

  • González, Sandra R.; Ie, Yutaka; Aso, Yoshio
  • Journal of the American Chemical Society, Vol. 133, Issue 41
  • DOI: 10.1021/ja2061903

Polarized Raman Spectroscopy of Oligothiophene Crystals To Determine Unit Cell Orientation
journal, May 2012

  • Heckel, John C.; Weisman, Andrew L.; Schneebeli, Severin T.
  • The Journal of Physical Chemistry A, Vol. 116, Issue 25
  • DOI: 10.1021/jp304192v

Infrared activity of photoexcitations in polythiophene
journal, August 1986

Photoinduced absorption and resonant Raman scattering of polythiophene
journal, February 1987

Photoexcitations in Regio-regular and Regio-random Polythiophene Films
journal, April 2003

Femtosecond–picosecond dynamics of the lowest excited singlet state in α-quinquethiophene
journal, November 1998

Resonant Raman spectroscopy on α-hexathiophene single crystals
journal, March 2004

Exciton Conformational Dynamics of Poly(3-hexylthiophene) (P3HT) in Solution from Time-Resolved Resonant-Raman Spectroscopy
journal, May 2012

  • Yu, Wenjian; Zhou, Jiawang; Bragg, Arthur E.
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 10
  • DOI: 10.1021/jz3003298

Ultrafast photo-induced nuclear relaxation of a conformationally disordered conjugated polymer probed with transient absorption and femtosecond stimulated Raman spectroscopies
journal, July 2014

  • Yu, Wenjian; Donohoo-Vallett, Paul J.; Zhou, Jiawang
  • The Journal of Chemical Physics, Vol. 141, Issue 4
  • DOI: 10.1063/1.4890326

Vibrational spectra of oligothiophenes as model of polythiophenes
journal, March 1991

  • Zerbi, G.; Chierichetti, B.; Ingänas, O.
  • The Journal of Chemical Physics, Vol. 94, Issue 6
  • DOI: 10.1063/1.460592

Structure and Optical Properties of Conjugated Oligomers from their Vibrational Spectra
book, May 1998

Conformational changes involved in the singlet-triplet transitions of biphenyl
journal, June 1967

  • Wagner, Peter John.
  • Journal of the American Chemical Society, Vol. 89, Issue 12
  • DOI: 10.1021/ja00988a004

Electronic structure and torsional potentials in ground and excited states of biphenyl, fulvalene, and related compounds
journal, September 1968

  • Imamura, Akira; Hoffmann, Roald
  • Journal of the American Chemical Society, Vol. 90, Issue 20
  • DOI: 10.1021/ja01022a008

Polarons, bipolarons, and solitons in conducting polymers
journal, October 1985

  • Bredas, Jean Luc; Street, G. Bryan
  • Accounts of Chemical Research, Vol. 18, Issue 10
  • DOI: 10.1021/ar00118a005

Triplet (T 1 ) state and radical cation resonance Raman investigation of biphenyl derivatives
journal, August 1989

  • Buntinx, G.; Poizat, O.
  • The Journal of Chemical Physics, Vol. 91, Issue 4
  • DOI: 10.1063/1.457023

Theoretical study of thiophene oligomers: Electronic excitations, relaxation energies, and nonlinear optical properties
journal, June 1993

  • Beljonne, D.; Shuai, Z.; Brédas, J. L.
  • The Journal of Chemical Physics, Vol. 98, Issue 11
  • DOI: 10.1063/1.464491

Raman spectra and structure of biphenyl isoatomers (the S0, S1, T1 states and the cation and anion radicals)
journal, July 1994

  • Sasaki, Yutaka; Hamaguchi, Hiro-o
  • Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 50, Issue 8-9
  • DOI: 10.1016/0584-8539(94)E0058-I

Femtosecond vibrational and torsional energy redistribution in photoexcited oligothiophenes
journal, March 1996

Observation and control of coherent torsional dynamics in a quinquethiophene molecule
journal, January 2010

  • Cirmi, Giovanni; Brida, Daniele; Gambetta, Alessio
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 28
  • DOI: 10.1039/c000505c

Magnetic Properties of Quinoidal Oligothiophenes: More Than Good Candidates for Ambipolar Organic Semiconductors?
journal, March 2006

  • Ponce Ortiz, R.; Casado, J.; Hernández, V.
  • Advanced Functional Materials, Vol. 16, Issue 4
  • DOI: 10.1002/adfm.200500404

On the Biradicaloid Nature of Long Quinoidal Oligothiophenes: Experimental Evidence Guided by Theoretical Studies
journal, December 2007

  • Ponce Ortiz, Rocío; Casado, Juan; Hernández, Víctor
  • Angewandte Chemie International Edition, Vol. 46, Issue 47
  • DOI: 10.1002/anie.200703244

Solitons in conducting polymers
journal, July 1988

Theoretical Study of Long Oligothiophene Dications:  Bipolaron vs Polaron Pair vs Triplet State
journal, August 2006

  • Zade, Sanjio S.; Bendikov, Michael
  • The Journal of Physical Chemistry B, Vol. 110, Issue 32
  • DOI: 10.1021/jp062748v

Joint theoretical and experimental study on the phosphorescence of 2,2′-bithiophene
journal, January 2014

  • Andrzejak, Marcin; Orzeł, Łukasz
  • Physical Chemistry Chemical Physics, Vol. 16, Issue 12
  • DOI: 10.1039/c3cp55221g

Toward Enabling Large-Scale Open-Shell Equation-of-Motion Coupled Cluster Calculations: Triplet States of β-Carotene
journal, June 2014

  • Hu, Han-Shi; Bhaskaran-Nair, Kiran; Aprà, Edoardo
  • The Journal of Physical Chemistry A, Vol. 118, Issue 39
  • DOI: 10.1021/jp5021214

Benchmarks for electronically excited states: Time-dependent density functional theory and density functional theory based multireference configuration interaction
journal, September 2008

  • Silva-Junior, Mario R.; Schreiber, Marko; Sauer, Stephan P. A.
  • The Journal of Chemical Physics, Vol. 129, Issue 10
  • DOI: 10.1063/1.2973541

Interchain Delocalization of Photoinduced Neutral and Charged States in Nanoaggregates of Lengthy Oligothiophenes
journal, June 2001

  • Apperloo, Joke J.; Janssen, René A. J.; Malenfant, Patrick R. L.
  • Journal of the American Chemical Society, Vol. 123, Issue 28
  • DOI: 10.1021/ja015862u
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    A synergic approach of X-ray powder diffraction and Raman spectroscopy for crystal structure determination of 2,3-thienoimide capped oligothiophenes
    journal, January 2018

    • Cappuccino, C.; Mazzeo, P. P.; Salzillo, T.
    • Physical Chemistry Chemical Physics, Vol. 20, Issue 5
    • DOI: 10.1039/c7cp06679a
      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: