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Title: Comparative Computational Study of Electronic Excitations of Neutral and Charged Small Oligothiophenes and Their Extrapolations Based on Simple Models

Abstract

This work reports electronic excitation energies of neutral and charged oligothiophenes (OTn) with repeat unit n = 2-6 computed by routinely used semiempirical and time-dependent density functional theory (TD-DFT) methods. More specifically, for OTn, OTn+, and OTn-, we calculated vertical transition energies for electronic absorption spectroscopy employing the Zerner’s version of intermediate neglect differential overlap method for structures optimized by the PM6 semiempirical method and the TD-DFT method with three different functionals, B3LYP, BVP86, and M06-2X, for structures optimized by the groundstate DFT method employing the same functionals. We also calculated vertical transition energies for the emission spectroscopy from the lowest singlet excited states by employing the TD-DFT method for the structures optimized for the lowest singlet excited states. In addition to computational results in vacuum, solution phase data calculated at the level of polarizable continuum model are reported and compared with available experimental data. Most of the data are fitted reasonably well by two simple model functions, one based on a Frenkel exciton theory and the other based on the model of independent electrons in a box with sinusoidal modulation of potential. Despite similar levels of fitting performance, the two models produce distinctively different asymptotic values of excitation energies.more » Comparison of these with available experimental and computational data suggests that the values based on the exciton model, while seemingly overestimating, are closer to true values than those based on the other model. This assessment is confirmed by additional calculations for a larger oligomer. The fitting parameters offer new means to understand the relationship between electronic excitations of OTs and their sizes and suggest the feasibility of constructing simple coarse-grained exciton-bath models applicable for aggregates of OTs.« less

Authors:
 [1];  [2]; ORCiD logo [2]
  1. Department of Chemistry and Biochemistry, Queens College, City University of New York, 65-30 Kissena Boulevard, Queens, New York 11367, United States
  2. Department of Chemistry and Biochemistry, Queens College, City University of New York, 65-30 Kissena Boulevard, Queens, New York 11367, United States, Ph.D. Programs in Chemistry and Physics, and Initiative for the Theoretical Sciences, Graduate Center, City University of New York, 365 Fifth Avenue, New York, New York 10016, United States
Publication Date:
Research Org.:
Queens College, City Univ. of New York, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1503369
Alternate Identifier(s):
OSTI ID: 1508799; OSTI ID: 1755118
Report Number(s):
DOE-Queens-1393-23
Journal ID: ISSN 2470-1343
Grant/Contract Number:  
SC0001393; CHE-1362926
Resource Type:
Published Article
Journal Name:
ACS Omega
Additional Journal Information:
Journal Name: ACS Omega Journal Volume: 4 Journal Issue: 3; Journal ID: ISSN 2470-1343
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; fluorescence; molecular structure; polythiophenes; potential energy; quantum mechanical methods; quantum transition; solvation; spectra; theory; Oligothiophene, Exciton energy, Size dependence

Citation Formats

Kowalczyk, Marta, Chen, Ning, and Jang, Seogjoo J. Comparative Computational Study of Electronic Excitations of Neutral and Charged Small Oligothiophenes and Their Extrapolations Based on Simple Models. United States: N. p., 2019. Web. doi:10.1021/acsomega.8b02972.
Kowalczyk, Marta, Chen, Ning, & Jang, Seogjoo J. Comparative Computational Study of Electronic Excitations of Neutral and Charged Small Oligothiophenes and Their Extrapolations Based on Simple Models. United States. https://doi.org/10.1021/acsomega.8b02972
Kowalczyk, Marta, Chen, Ning, and Jang, Seogjoo J. Mon . "Comparative Computational Study of Electronic Excitations of Neutral and Charged Small Oligothiophenes and Their Extrapolations Based on Simple Models". United States. https://doi.org/10.1021/acsomega.8b02972.
@article{osti_1503369,
title = {Comparative Computational Study of Electronic Excitations of Neutral and Charged Small Oligothiophenes and Their Extrapolations Based on Simple Models},
author = {Kowalczyk, Marta and Chen, Ning and Jang, Seogjoo J.},
abstractNote = {This work reports electronic excitation energies of neutral and charged oligothiophenes (OTn) with repeat unit n = 2-6 computed by routinely used semiempirical and time-dependent density functional theory (TD-DFT) methods. More specifically, for OTn, OTn+, and OTn-, we calculated vertical transition energies for electronic absorption spectroscopy employing the Zerner’s version of intermediate neglect differential overlap method for structures optimized by the PM6 semiempirical method and the TD-DFT method with three different functionals, B3LYP, BVP86, and M06-2X, for structures optimized by the groundstate DFT method employing the same functionals. We also calculated vertical transition energies for the emission spectroscopy from the lowest singlet excited states by employing the TD-DFT method for the structures optimized for the lowest singlet excited states. In addition to computational results in vacuum, solution phase data calculated at the level of polarizable continuum model are reported and compared with available experimental data. Most of the data are fitted reasonably well by two simple model functions, one based on a Frenkel exciton theory and the other based on the model of independent electrons in a box with sinusoidal modulation of potential. Despite similar levels of fitting performance, the two models produce distinctively different asymptotic values of excitation energies. Comparison of these with available experimental and computational data suggests that the values based on the exciton model, while seemingly overestimating, are closer to true values than those based on the other model. This assessment is confirmed by additional calculations for a larger oligomer. The fitting parameters offer new means to understand the relationship between electronic excitations of OTs and their sizes and suggest the feasibility of constructing simple coarse-grained exciton-bath models applicable for aggregates of OTs.},
doi = {10.1021/acsomega.8b02972},
journal = {ACS Omega},
number = 3,
volume = 4,
place = {United States},
year = {2019},
month = {3}
}

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Works referenced in this record:

Density-functional study of the evolution of the electronic structure of oligomers of thiophene: Towards a model Hamiltonian
journal, March 2001


Laser flash photolysis study on the photoinduced reactions of 3,3′-bridged bithiophenes
journal, January 1998

  • Fujitsuka, Mamoru; Sato, Tadatake; Sezaki, Fumiyasu
  • Journal of the Chemical Society, Faraday Transactions, Vol. 94, Issue 22
  • DOI: 10.1039/a806072j

Theoretical Investigation of Excited States of Oligothiophene Anions
journal, July 2008

  • Alkan, Fahri; Salzner, Ulrike
  • The Journal of Physical Chemistry A, Vol. 112, Issue 27
  • DOI: 10.1021/jp711135e

Time-dependent density-functional calculations of S[sub 0]–S[sub 1] transition energies of poly(p-phenylene vinylene)
journal, January 2004

  • Han, Young-Kyu; Lee, Sang Uck
  • The Journal of Chemical Physics, Vol. 121, Issue 1
  • DOI: 10.1063/1.1737297

High-Performance Semiconducting Polythiophenes for Organic Thin-Film Transistors
journal, March 2004

  • Ong, Beng S.; Wu, Yiliang; Liu, Ping
  • Journal of the American Chemical Society, Vol. 126, Issue 11, p. 3378-3379
  • DOI: 10.1021/ja039772w

Density-functional exchange-energy approximation with correct asymptotic behavior
journal, September 1988


An all-organic "soft" thin film transistor with very high carrier mobility
journal, December 1990


New parametrization scheme for the resonance integrals (H??) within the INDO/1 approximation. Main group elements
journal, January 2000


Polythiophene: From Fundamental Perspectives to Applications
journal, November 2017

  • Kaloni, Thaneshwor P.; Giesbrecht, Patrick K.; Schreckenbach, Georg
  • Chemistry of Materials, Vol. 29, Issue 24
  • DOI: 10.1021/acs.chemmater.7b03035

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

Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis
journal, August 1980

  • Vosko, S. H.; Wilk, L.; Nusair, M.
  • Canadian Journal of Physics, Vol. 58, Issue 8
  • DOI: 10.1139/p80-159

Size-Dependent Properties of Oligothiophenes by Picosecond Time-Resolved Spectroscopy
journal, November 1995

  • Grebner, D.; Helbig, M.; Rentsch, S.
  • The Journal of Physical Chemistry, Vol. 99, Issue 46
  • DOI: 10.1021/j100046a027

Nature of optical transitions in conjugated oligomers. II. Theoretical characterization of neutral and doped oligothiophenes
journal, July 1995

  • Cornil, J.; Beljonne, D.; Brédas, J. L.
  • The Journal of Chemical Physics, Vol. 103, Issue 2
  • DOI: 10.1063/1.470065

?Thiophene octamer as a new class of photo-active material for photoelectrical conversion
journal, July 1995


A Quantum‐Mechanical Theory of Light Absorption of Organic Dyes and Similar Compounds
journal, December 1949

  • Kuhn, Hans
  • The Journal of Chemical Physics, Vol. 17, Issue 12
  • DOI: 10.1063/1.1747143

No single DFT method can predict Raman cross-sections, frequencies and electronic absorption maxima of oligothiophenes
journal, September 2017


Functional Oligothiophenes: Molecular Design for Multidimensional Nanoarchitectures and Their Applications
journal, March 2009

  • Mishra, Amaresh; Ma, Chang-Qi; Bäuerle, Peter
  • Chemical Reviews, Vol. 109, Issue 3
  • DOI: 10.1021/cr8004229

Nobel Lecture: Semiconducting and metallic polymers: The fourth generation of polymeric materials
journal, September 2001


Quantitative prediction of optical excitations in conjugated organic oligomers: A density functional theory study
journal, September 2002

  • Pogantsch, A.; Heimel, G.; Zojer, E.
  • The Journal of Chemical Physics, Vol. 117, Issue 12
  • DOI: 10.1063/1.1502244

Optical properties of disordered molecular aggregates: A numerical study
journal, December 1991

  • Fidder, Henk; Knoester, Jasper; Wiersma, Douwe A.
  • The Journal of Chemical Physics, Vol. 95, Issue 11
  • DOI: 10.1063/1.461317

Experimental and theoretical investigations of absorption and emission spectra of the light-emitting polymer MEH-PPV in solution
journal, January 2000


Fluorescence and absorption spectra of oligophenylenevinylenes: Vibronic coupling, band shapes, and solvatochromism
journal, January 2002

  • Gierschner, Johannes; Mack, Hans-Georg; Lüer, Larry
  • The Journal of Chemical Physics, Vol. 116, Issue 19
  • DOI: 10.1063/1.1469612

Energy Gaps of α,α‘-Substituted Oligothiophenes from Semiempirical, Ab Initio, and Density Functional Methods
journal, September 2000

  • De Oliveira, Marcos A.; Duarte, Hélio A.; Pernaut, Jean-Michel
  • The Journal of Physical Chemistry A, Vol. 104, Issue 35
  • DOI: 10.1021/jp001252p

Comment on “Time-Dependent Density Functional Study of Electroluminescent Polymers”
journal, October 2004

  • Han, Young-Kyu
  • The Journal of Physical Chemistry A, Vol. 108, Issue 42
  • DOI: 10.1021/jp037746e

Improved quantum mechanical study of the potential energy surface for the bithiophene molecule
journal, September 2000

  • Duarte, Hélio A.; Dos Santos, Hélio F.; Rocha, Willian R.
  • The Journal of Chemical Physics, Vol. 113, Issue 10
  • DOI: 10.1063/1.1288383

Charge storage in doped poly(thiophene): Optical and electrochemical studies
journal, July 1984


Photophysical studies of mixed furan, pyrrole, and thiophene-containing oligomers with three and five rings
journal, September 2002

  • Seixas de Melo, J.; Elisei, Fausto; Becker, Ralph S.
  • The Journal of Chemical Physics, Vol. 117, Issue 9
  • DOI: 10.1063/1.1498115

Optical Bandgaps of π-Conjugated Organic Materials at the Polymer Limit: Experiment and Theory
journal, January 2007

  • Gierschner, J.; Cornil, J.; Egelhaaf, H. -J.
  • Advanced Materials, Vol. 19, Issue 2
  • DOI: 10.1002/adma.200600277

Conformational analysis and electronic properties of bithiophene and terthiophene in their ground state as well as in their first excited singlet and triplet states
journal, February 1996


Theoretical study of the size confinement effect in linear π-conjugated oligomers
journal, December 2007


Light-Emitting Polythiophenes
journal, October 2005

  • Perepichka, I. F.; Perepichka, D. F.; Meng, H.
  • Advanced Materials, Vol. 17, Issue 19
  • DOI: 10.1002/adma.200500461

Quantum Mechanical Continuum Solvation Models
journal, August 2005

  • Tomasi, Jacopo; Mennucci, Benedetta; Cammi, Roberto
  • Chemical Reviews, Vol. 105, Issue 8
  • DOI: 10.1021/cr9904009

A polymer tandem solar cell with 10.6% power conversion efficiency
journal, February 2013

  • You, Jingbi; Dou, Letian; Yoshimura, Ken
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms2411

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

Optical spectra from molecules to crystals: Insight from many-body perturbation theory
journal, November 2015


Computational reinvestigation of the bithiophene torsion potential
journal, September 2003


The generation and spectral characterization of oligothiophenes radical cations. A pulse radiolysis investigation
journal, March 1999


Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965


Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Optical absorption spectra of linear and cyclic thiophenes—selection rules manifestation
journal, December 2004


Organic solar cells: A new look at traditional models
journal, January 2011

  • Servaites, Jonathan D.; Ratner, Mark A.; Marks, Tobin J.
  • Energy & Environmental Science, Vol. 4, Issue 11
  • DOI: 10.1039/c1ee01663f

Single-Reference ab Initio Methods for the Calculation of Excited States of Large Molecules
journal, November 2005

  • Dreuw, Andreas; Head-Gordon, Martin
  • Chemical Reviews, Vol. 105, Issue 11
  • DOI: 10.1021/cr0505627

Theoretical Investigation of the Mechanism and Dynamics of Intramolecular Coherent Resonance Energy Transfer in Soft Molecules: A Case Study of Dithia-anthracenophane
journal, December 2010

  • Yang, Lei; Caprasecca, Stefano; Mennucci, Benedetta
  • Journal of the American Chemical Society, Vol. 132, Issue 47
  • DOI: 10.1021/ja103303u

Investigation of Charge Carriers in Doped Thiophene Oligomers through Theoretical Modeling of their UV/Vis Spectra
journal, June 2008

  • Salzner, Ulrike
  • The Journal of Physical Chemistry A, Vol. 112, Issue 24
  • DOI: 10.1021/jp800606m

The Bethe–Salpeter equation in chemistry: relations with TD-DFT, applications and challenges
journal, January 2018

  • Blase, Xavier; Duchemin, Ivan; Jacquemin, Denis
  • Chemical Society Reviews, Vol. 47, Issue 3
  • DOI: 10.1039/C7CS00049A

H- and J-Aggregate Behavior in Polymeric Semiconductors
journal, April 2014


Accurate Prediction of Band Gaps in Neutral Heterocyclic Conjugated Polymers
journal, November 2002

  • Hutchison, Geoffrey R.; Ratner, Mark A.; Marks, Tobin J.
  • The Journal of Physical Chemistry A, Vol. 106, Issue 44
  • DOI: 10.1021/jp025999m

Electronic and optical properties of functionalized carbon chains with the localized Hartree–Fock and conventional Kohn–Sham methods
journal, February 2005


Effect of dopant on the physicochemical and electrical properties of organic conducting polymers
journal, June 1983

  • Tourillon, G.; Garnier, F.
  • The Journal of Physical Chemistry, Vol. 87, Issue 13
  • DOI: 10.1021/j100236a010

Density-functional approximation for the correlation energy of the inhomogeneous electron gas
journal, June 1986


Organic Semiconducting Oligomers for Use in Thin Film Transistors
journal, April 2007

  • Murphy, Amanda R.; Fréchet, Jean M. J.
  • Chemical Reviews, Vol. 107, Issue 4
  • DOI: 10.1021/cr0501386

Density-Functional Theory for Time-Dependent Systems
journal, March 1984


Excitons in Conjugated Oligomer Aggregates, Films, and Crystals
journal, May 2006


Failure of density-functional theory and time-dependent density-functional theory for large extended π systems
journal, September 2002

  • Cai, Zheng-Li; Sendt, Karina; Reimers, Jeffrey R.
  • The Journal of Chemical Physics, Vol. 117, Issue 12
  • DOI: 10.1063/1.1501131

Recent Advances in Bulk Heterojunction Polymer Solar Cells
journal, August 2015


The solvatochromic effect on some oligothiophene radical cations: a pulse radiolysis and semiempirical investigation
journal, June 2003


Solution-Processed Organic n-Type Thin-Film Transistors
journal, December 2003

  • Waldauf, C.; Schilinsky, P.; Perisutti, M.
  • Advanced Materials, Vol. 15, Issue 24
  • DOI: 10.1002/adma.200305623

Excitonic coupling in polythiophenes: Comparison of different calculation methods
journal, February 2004

  • Beenken, Wichard J. D.; Pullerits, Tõnu
  • The Journal of Chemical Physics, Vol. 120, Issue 5
  • DOI: 10.1063/1.1636460

Optimization of parameters for semiempirical methods V: Modification of NDDO approximations and application to 70 elements
journal, September 2007


Electroluminescence from oligothiophene-based light-emitting devices
journal, December 1993

  • Geiger, Friedhelm; Stoldt, Marion; Schweizer, Heinz
  • Advanced Materials, Vol. 5, Issue 12
  • DOI: 10.1002/adma.19930051210

The electroluminescence of organic materials
journal, January 2000

  • Mitschke, Ullrich; Bäuerle, Peter
  • Journal of Materials Chemistry, Vol. 10, Issue 7
  • DOI: 10.1039/a908713c

For the Bright Future-Bulk Heterojunction Polymer Solar Cells with Power Conversion Efficiency of 7.4%
journal, May 2010

  • Liang, Yongye; Xu, Zheng; Xia, Jiangbin
  • Advanced Materials, Vol. 22, Issue 20, p. E135-E138
  • DOI: 10.1002/adma.200903528

Does the donor–acceptor concept work for designing synthetic metals?: III. Theoretical investigation of copolymers between quinoid acceptors and aromatic donors
journal, January 2006

  • Salzner, Ulrike; Karaltı, Ozan; Durdaği, Serdar
  • Journal of Molecular Modeling, Vol. 12, Issue 5
  • DOI: 10.1007/s00894-005-0046-2

Structural order in conjugated oligothiophenes and its implications on opto-electronic devices
journal, January 2000

  • Fichou, Denis
  • Journal of Materials Chemistry, Vol. 10, Issue 3
  • DOI: 10.1039/a908312j

Excited States of Dicyanovinyl-Substituted Oligothiophenes from Many-Body Green’s Functions Theory
journal, February 2012

  • Baumeier, Björn; Andrienko, Denis; Ma, Yuchen
  • Journal of Chemical Theory and Computation, Vol. 8, Issue 3
  • DOI: 10.1021/ct2008999

Charge-Transfer and Energy-Transfer Processes in π-Conjugated Oligomers and Polymers:  A Molecular Picture
journal, November 2004

  • Brédas, Jean-Luc; Beljonne, David; Coropceanu, Veaceslav
  • Chemical Reviews, Vol. 104, Issue 11
  • DOI: 10.1021/cr040084k

Theoretical studies and spectroscopic investigations of ground and excited electronic states of thiophene oligomers
journal, December 1995


Spectroscopic Units in Conjugated Polymers:  A Quantum Chemically Founded Concept?
journal, May 2004

  • Beenken, Wichard J. D.; Pullerits, Tõnu
  • The Journal of Physical Chemistry B, Vol. 108, Issue 20
  • DOI: 10.1021/jp037332l

Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994

  • Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.
  • The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627
  • DOI: 10.1021/j100096a001

Reviewing Extrapolation Procedures of the Electronic Properties on the π-Conjugated Polymer Limit
journal, July 2012

  • Torras, Juan; Casanovas, Jordi; Alemán, Carlos
  • The Journal of Physical Chemistry A, Vol. 116, Issue 28
  • DOI: 10.1021/jp303584b

Qualitatively Correct Charge-Transfer Excitation Energies in HeH + by Time-Dependent Density-Functional Theory Due to Exact Exchange Kohn−Sham Eigenvalue Differences
journal, March 2009

  • Gimon, Tino; Ipatov, Andrey; Heßelmann, Andreas
  • Journal of Chemical Theory and Computation, Vol. 5, Issue 4
  • DOI: 10.1021/ct800539a

Electronic Energy Gaps for π-Conjugated Oligomers and Polymers Calculated with Density Functional Theory
journal, February 2014

  • Sun, Haitao; Autschbach, Jochen
  • Journal of Chemical Theory and Computation, Vol. 10, Issue 3
  • DOI: 10.1021/ct4009975