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

Kowalczyk, Marta; Chen, Ning; Jang, Seogjoo J.

doi:10.1021/acsomega.8b02972

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

Journal Article · Mon Mar 25 00:00:00 EDT 2019 · ACS Omega

DOI:https://doi.org/10.1021/acsomega.8b02972· OSTI ID:1503369

Kowalczyk, Marta ^[1]; Chen, Ning ^[2];

^[2]

Department of Chemistry and Biochemistry, Queens College, City University of New York, 65-30 Kissena Boulevard, Queens, New York 11367, United States
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

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.

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Research Organization:: Queens College, City Univ. of New York, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0001393; CHE-1362926

OSTI ID:: 1503369

Alternate ID(s):: OSTI ID: 1508799; OSTI ID: 1755118

Report Number(s):: DOE-Queens-1393-23

Journal Information:: ACS Omega, Journal Name: ACS Omega Vol. 4 Journal Issue: 3; ISSN 2470-1343

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 2 works

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References (69)

Laser flash photolysis study on the photoinduced reactions of 3,3′-bridged bithiophenes Fujitsuka, Mamoru; Sato, Tadatake; Sezaki, Fumiyasu Journal of the Chemical Society, Faraday Transactions, Vol. 94, Issue 22 https://doi.org/10.1039/a806072j	journal	January 1998
Theoretical Investigation of Excited States of Oligothiophene Anions Alkan, Fahri; Salzner, Ulrike The Journal of Physical Chemistry A, Vol. 112, Issue 27 https://doi.org/10.1021/jp711135e	journal	July 2008
Time-dependent density-functional calculations of S[sub 0]–S[sub 1] transition energies of poly(p-phenylene vinylene) Han, Young-Kyu; Lee, Sang Uck The Journal of Chemical Physics, Vol. 121, Issue 1 https://doi.org/10.1063/1.1737297	journal	January 2004
High-Performance Semiconducting Polythiophenes for Organic Thin-Film Transistors Ong, Beng S.; Wu, Yiliang; Liu, Ping Journal of the American Chemical Society, Vol. 126, Issue 11, p. 3378-3379 https://doi.org/10.1021/ja039772w	journal	March 2004
Density-functional exchange-energy approximation with correct asymptotic behavior Becke, A. D. Physical Review A, Vol. 38, Issue 6 https://doi.org/10.1103/PhysRevA.38.3098	journal	September 1988
An all-organic "soft" thin film transistor with very high carrier mobility Garnier, Francis; Horowitz, Gilles; Peng, Xuezhou Advanced Materials, Vol. 2, Issue 12 https://doi.org/10.1002/adma.19900021207	journal	December 1990
New parametrization scheme for the resonance integrals (H??) within the INDO/1 approximation. Main group elements Da Motta Neto, Joaquim Delphino; Zerner, Michael C. International Journal of Quantum Chemistry, Vol. 81, Issue 3 https://doi.org/10.1002/1097-461X(2001)81:3<187::AID-QUA1>3.0.CO;2-B	journal	January 2000
Polythiophene: From Fundamental Perspectives to Applications Kaloni, Thaneshwor P.; Giesbrecht, Patrick K.; Schreckenbach, Georg Chemistry of Materials, Vol. 29, Issue 24 https://doi.org/10.1021/acs.chemmater.7b03035	journal	November 2017
Theoretical study of thiophene oligomers: Electronic excitations, relaxation energies, and nonlinear optical properties Beljonne, D.; Shuai, Z.; Brédas, J. L. The Journal of Chemical Physics, Vol. 98, Issue 11 https://doi.org/10.1063/1.464491	journal	June 1993
Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis Vosko, S. H.; Wilk, L.; Nusair, M. Canadian Journal of Physics, Vol. 58, Issue 8 https://doi.org/10.1139/p80-159	journal	August 1980
Size-Dependent Properties of Oligothiophenes by Picosecond Time-Resolved Spectroscopy Grebner, D.; Helbig, M.; Rentsch, S. The Journal of Physical Chemistry, Vol. 99, Issue 46 https://doi.org/10.1021/j100046a027	journal	November 1995
Nature of optical transitions in conjugated oligomers. II. Theoretical characterization of neutral and doped oligothiophenes Cornil, J.; Beljonne, D.; Brédas, J. L. The Journal of Chemical Physics, Vol. 103, Issue 2 https://doi.org/10.1063/1.470065	journal	July 1995
?Thiophene octamer as a new class of photo-active material for photoelectrical conversion Noma, Naoki; Tsuzuki, Toshimitsu; Shirota, Yasuhiko Advanced Materials, Vol. 7, Issue 7 https://doi.org/10.1002/adma.19950070709	journal	July 1995
A Quantum‐Mechanical Theory of Light Absorption of Organic Dyes and Similar Compounds Kuhn, Hans The Journal of Chemical Physics, Vol. 17, Issue 12 https://doi.org/10.1063/1.1747143	journal	December 1949
No single DFT method can predict Raman cross-sections, frequencies and electronic absorption maxima of oligothiophenes Huff, Gregory S.; Gallaher, Joseph K.; Hodgkiss, Justin M. Synthetic Metals, Vol. 231 https://doi.org/10.1016/j.synthmet.2017.06.009	journal	September 2017
Functional Oligothiophenes: Molecular Design for Multidimensional Nanoarchitectures and Their Applications ^† Mishra, Amaresh; Ma, Chang-Qi; Bäuerle, Peter Chemical Reviews, Vol. 109, Issue 3 https://doi.org/10.1021/cr8004229	journal	March 2009
Nobel Lecture: Semiconducting and metallic polymers: The fourth generation of polymeric materials Heeger, Alan J. Reviews of Modern Physics, Vol. 73, Issue 3 https://doi.org/10.1103/RevModPhys.73.681	journal	September 2001
Quantitative prediction of optical excitations in conjugated organic oligomers: A density functional theory study Pogantsch, A.; Heimel, G.; Zojer, E. The Journal of Chemical Physics, Vol. 117, Issue 12 https://doi.org/10.1063/1.1502244	journal	September 2002
Optical properties of disordered molecular aggregates: A numerical study Fidder, Henk; Knoester, Jasper; Wiersma, Douwe A. The Journal of Chemical Physics, Vol. 95, Issue 11 https://doi.org/10.1063/1.461317	journal	December 1991
Experimental and theoretical investigations of absorption and emission spectra of the light-emitting polymer MEH-PPV in solution Chang, R.; Hsu, J. H.; Fann, W. S. Chemical Physics Letters, Vol. 317, Issue 1-2 https://doi.org/10.1016/S0009-2614(99)01356-1	journal	January 2000
Fluorescence and absorption spectra of oligophenylenevinylenes: Vibronic coupling, band shapes, and solvatochromism Gierschner, Johannes; Mack, Hans-Georg; Lüer, Larry The Journal of Chemical Physics, Vol. 116, Issue 19 https://doi.org/10.1063/1.1469612	journal	January 2002
Energy Gaps of α,α‘-Substituted Oligothiophenes from Semiempirical, Ab Initio, and Density Functional Methods De Oliveira, Marcos A.; Duarte, Hélio A.; Pernaut, Jean-Michel The Journal of Physical Chemistry A, Vol. 104, Issue 35 https://doi.org/10.1021/jp001252p	journal	September 2000
Comment on “Time-Dependent Density Functional Study of Electroluminescent Polymers” Han, Young-Kyu The Journal of Physical Chemistry A, Vol. 108, Issue 42 https://doi.org/10.1021/jp037746e	journal	October 2004
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals Zhao, Yan; Truhlar, Donald G. Theoretical Chemistry Accounts, Vol. 120, Issue 1-3 https://doi.org/10.1007/s00214-007-0310-x	journal	July 2007
Improved quantum mechanical study of the potential energy surface for the bithiophene molecule Duarte, Hélio A.; Dos Santos, Hélio F.; Rocha, Willian R. The Journal of Chemical Physics, Vol. 113, Issue 10 https://doi.org/10.1063/1.1288383	journal	September 2000
Photophysical studies of mixed furan, pyrrole, and thiophene-containing oligomers with three and five rings Seixas de Melo, J.; Elisei, Fausto; Becker, Ralph S. The Journal of Chemical Physics, Vol. 117, Issue 9 https://doi.org/10.1063/1.1498115	journal	September 2002
Optical Bandgaps of π-Conjugated Organic Materials at the Polymer Limit: Experiment and Theory Gierschner, J.; Cornil, J.; Egelhaaf, H. -J. Advanced Materials, Vol. 19, Issue 2 https://doi.org/10.1002/adma.200600277	journal	January 2007
Conformational analysis and electronic properties of bithiophene and terthiophene in their ground state as well as in their first excited singlet and triplet states Belletête, Michel; Di Césare, Nicolas; Leclerc, Mario Chemical Physics Letters, Vol. 250, Issue 1 https://doi.org/10.1016/0009-2614(95)01444-6	journal	February 1996
Theoretical study of the size confinement effect in linear π-conjugated oligomers Bednarz, Mariusz; Reineker, Peter; Mena-Osteritz, Elena Chemical Physics, Vol. 342, Issue 1-3 https://doi.org/10.1016/j.chemphys.2007.09.052	journal	December 2007
Light-Emitting Polythiophenes Perepichka, I. F.; Perepichka, D. F.; Meng, H. Advanced Materials, Vol. 17, Issue 19 https://doi.org/10.1002/adma.200500461	journal	October 2005
Quantum Mechanical Continuum Solvation Models Tomasi, Jacopo; Mennucci, Benedetta; Cammi, Roberto Chemical Reviews, Vol. 105, Issue 8 https://doi.org/10.1021/cr9904009	journal	August 2005
A polymer tandem solar cell with 10.6% power conversion efficiency You, Jingbi; Dou, Letian; Yoshimura, Ken Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms2411	journal	February 2013
Theoretical Study of Long Oligothiophene Dications: Bipolaron vs Polaron Pair vs Triplet State Zade, Sanjio S.; Bendikov, Michael The Journal of Physical Chemistry B, Vol. 110, Issue 32 https://doi.org/10.1021/jp062748v	journal	August 2006
Tests of the RPBE, revPBE, τ-HCTHhyb, ωB97X-D, and MOHLYP density functional approximations and 29 others against representative databases for diverse bond energies and barrier heights in catalysis Yang, Ke; Zheng, Jingjing; Zhao, Yan The Journal of Chemical Physics, Vol. 132, Issue 16 https://doi.org/10.1063/1.3382342	journal	April 2010
Optical spectra from molecules to crystals: Insight from many-body perturbation theory Cocchi, Caterina; Draxl, Claudia Physical Review B, Vol. 92, Issue 20 https://doi.org/10.1103/PhysRevB.92.205126	journal	November 2015
Computational reinvestigation of the bithiophene torsion potential Raos, Guido; Famulari, Antonino; Marcon, Valentina Chemical Physics Letters, Vol. 379, Issue 3-4 https://doi.org/10.1016/j.cplett.2003.08.060	journal	September 2003
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
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Optical absorption spectra of linear and cyclic thiophenes—selection rules manifestation Bednarz, Mariusz; Reineker, Peter; Mena-Osteritz, Elena Journal of Luminescence, Vol. 110, Issue 4 https://doi.org/10.1016/j.jlumin.2004.08.013	journal	December 2004
Organic solar cells: A new look at traditional models Servaites, Jonathan D.; Ratner, Mark A.; Marks, Tobin J. Energy & Environmental Science, Vol. 4, Issue 11 https://doi.org/10.1039/c1ee01663f	journal	January 2011
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
Theoretical Investigation of the Mechanism and Dynamics of Intramolecular Coherent Resonance Energy Transfer in Soft Molecules: A Case Study of Dithia-anthracenophane Yang, Lei; Caprasecca, Stefano; Mennucci, Benedetta Journal of the American Chemical Society, Vol. 132, Issue 47 https://doi.org/10.1021/ja103303u	journal	December 2010
Investigation of Charge Carriers in Doped Thiophene Oligomers through Theoretical Modeling of their UV/Vis Spectra Salzner, Ulrike The Journal of Physical Chemistry A, Vol. 112, Issue 24 https://doi.org/10.1021/jp800606m	journal	June 2008
The Bethe–Salpeter equation in chemistry: relations with TD-DFT, applications and challenges Blase, Xavier; Duchemin, Ivan; Jacquemin, Denis Chemical Society Reviews, Vol. 47, Issue 3 https://doi.org/10.1039/C7CS00049A	journal	January 2018
H- and J-Aggregate Behavior in Polymeric Semiconductors Spano, Frank C.; Silva, Carlos Annual Review of Physical Chemistry, Vol. 65, Issue 1 https://doi.org/10.1146/annurev-physchem-040513-103639	journal	April 2014
Accurate Prediction of Band Gaps in Neutral Heterocyclic Conjugated Polymers Hutchison, Geoffrey R.; Ratner, Mark A.; Marks, Tobin J. The Journal of Physical Chemistry A, Vol. 106, Issue 44 https://doi.org/10.1021/jp025999m	journal	November 2002
Electronic and optical properties of functionalized carbon chains with the localized Hartree–Fock and conventional Kohn–Sham methods Weimer, Martin; Hieringer, Wolfgang; Sala, Fabio Della Chemical Physics, Vol. 309, Issue 1 https://doi.org/10.1016/j.chemphys.2004.05.026	journal	February 2005
Effect of dopant on the physicochemical and electrical properties of organic conducting polymers Tourillon, G.; Garnier, F. The Journal of Physical Chemistry, Vol. 87, Issue 13 https://doi.org/10.1021/j100236a010	journal	June 1983
Organic Semiconducting Oligomers for Use in Thin Film Transistors Murphy, Amanda R.; Fréchet, Jean M. J. Chemical Reviews, Vol. 107, Issue 4 https://doi.org/10.1021/cr0501386	journal	April 2007
Density-Functional Theory for Time-Dependent Systems Runge, Erich; Gross, E. K. U. Physical Review Letters, Vol. 52, Issue 12 https://doi.org/10.1103/PhysRevLett.52.997	journal	March 1984
Excitons in Conjugated Oligomer Aggregates, Films, and Crystals Spano, Frank C. Annual Review of Physical Chemistry, Vol. 57, Issue 1 https://doi.org/10.1146/annurev.physchem.57.032905.104557	journal	May 2006
Failure of density-functional theory and time-dependent density-functional theory for large extended π systems Cai, Zheng-Li; Sendt, Karina; Reimers, Jeffrey R. The Journal of Chemical Physics, Vol. 117, Issue 12 https://doi.org/10.1063/1.1501131	journal	September 2002
Recent Advances in Bulk Heterojunction Polymer Solar Cells Lu, Luyao; Zheng, Tianyue; Wu, Qinghe Chemical Reviews, Vol. 115, Issue 23 https://doi.org/10.1021/acs.chemrev.5b00098	journal	August 2015
Solution-Processed Organic n-Type Thin-Film Transistors Waldauf, C.; Schilinsky, P.; Perisutti, M. Advanced Materials, Vol. 15, Issue 24 https://doi.org/10.1002/adma.200305623	journal	December 2003
Excitonic coupling in polythiophenes: Comparison of different calculation methods Beenken, Wichard J. D.; Pullerits, Tõnu The Journal of Chemical Physics, Vol. 120, Issue 5 https://doi.org/10.1063/1.1636460	journal	February 2004
Optimization of parameters for semiempirical methods V: Modification of NDDO approximations and application to 70 elements Stewart, James J. P. Journal of Molecular Modeling, Vol. 13, Issue 12 https://doi.org/10.1007/s00894-007-0233-4	journal	September 2007
Electroluminescence from oligothiophene-based light-emitting devices Geiger, Friedhelm; Stoldt, Marion; Schweizer, Heinz Advanced Materials, Vol. 5, Issue 12 https://doi.org/10.1002/adma.19930051210	journal	December 1993
The electroluminescence of organic materials Mitschke, Ullrich; Bäuerle, Peter Journal of Materials Chemistry, Vol. 10, Issue 7 https://doi.org/10.1039/a908713c	journal	January 2000
For the Bright Future-Bulk Heterojunction Polymer Solar Cells with Power Conversion Efficiency of 7.4% Liang, Yongye; Xu, Zheng; Xia, Jiangbin Advanced Materials, Vol. 22, Issue 20, p. E135-E138 https://doi.org/10.1002/adma.200903528	journal	May 2010
Does the donor–acceptor concept work for designing synthetic metals?: III. Theoretical investigation of copolymers between quinoid acceptors and aromatic donors Salzner, Ulrike; Karaltı, Ozan; Durdaği, Serdar Journal of Molecular Modeling, Vol. 12, Issue 5 https://doi.org/10.1007/s00894-005-0046-2	journal	January 2006
Structural order in conjugated oligothiophenes and its implications on opto-electronic devices Fichou, Denis Journal of Materials Chemistry, Vol. 10, Issue 3 https://doi.org/10.1039/a908312j	journal	January 2000
Excited States of Dicyanovinyl-Substituted Oligothiophenes from Many-Body Green’s Functions Theory Baumeier, Björn; Andrienko, Denis; Ma, Yuchen Journal of Chemical Theory and Computation, Vol. 8, Issue 3 https://doi.org/10.1021/ct2008999	journal	February 2012
Charge-Transfer and Energy-Transfer Processes in π-Conjugated Oligomers and Polymers: A Molecular Picture Brédas, Jean-Luc; Beljonne, David; Coropceanu, Veaceslav Chemical Reviews, Vol. 104, Issue 11 https://doi.org/10.1021/cr040084k	journal	November 2004
Theoretical studies and spectroscopic investigations of ground and excited electronic states of thiophene oligomers Colditz, R.; Grebner, D.; Helbig, M. Chemical Physics, Vol. 201, Issue 2-3 https://doi.org/10.1016/0301-0104(95)00280-4	journal	December 1995
Spectroscopic Units in Conjugated Polymers: A Quantum Chemically Founded Concept? Beenken, Wichard J. D.; Pullerits, Tõnu The Journal of Physical Chemistry B, Vol. 108, Issue 20 https://doi.org/10.1021/jp037332l	journal	May 2004
Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F. The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627 https://doi.org/10.1021/j100096a001	journal	November 1994
Reviewing Extrapolation Procedures of the Electronic Properties on the π-Conjugated Polymer Limit Torras, Juan; Casanovas, Jordi; Alemán, Carlos The Journal of Physical Chemistry A, Vol. 116, Issue 28 https://doi.org/10.1021/jp303584b	journal	July 2012
Qualitatively Correct Charge-Transfer Excitation Energies in HeH ⁺ by Time-Dependent Density-Functional Theory Due to Exact Exchange Kohn−Sham Eigenvalue Differences Gimon, Tino; Ipatov, Andrey; Heßelmann, Andreas Journal of Chemical Theory and Computation, Vol. 5, Issue 4 https://doi.org/10.1021/ct800539a	journal	March 2009
Electronic Energy Gaps for π-Conjugated Oligomers and Polymers Calculated with Density Functional Theory Sun, Haitao; Autschbach, Jochen Journal of Chemical Theory and Computation, Vol. 10, Issue 3 https://doi.org/10.1021/ct4009975	journal	February 2014

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

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