Optical Spectra of Oligofurans: A Theoretical Approach to the Transition Energies, Reorganization Energies, and the Vibronic Activity
Abstract
:1. Introduction
2. Computational Details
3. Results
3.1. Transition Energies and Reorganization Energies
3.2. Theoretical Modeling of the Optical Spectra
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Sample Availability
References
- Zhang, L.; Colella, N.S.; Cherniawski, B.P.; Mannsfeld, S.C.B.; Briseno, A.L. Oligothiophene semiconductors: Synthesis, characterization, and applications for organic devices. ACS Appl. Mater. Interfaces 2014, 68, 5327–5343. [Google Scholar] [CrossRef] [PubMed]
- Gebers, J.; Özen, B.; Hartmann, L.; Schaer, M.; Suárez, S.; Bugnon, P.; Scopelliti, R.; Steinrück, H.-G.; Konovalov, O.V.; Magerl, A.; et al. Crystallization and OFET Performance of a Hydrogen-Bonded Quaterthiophene. Chem. Eur. J. 2020, 26, 10265. [Google Scholar] [CrossRef] [PubMed]
- Reese, C.; Roberts, M.E.; Parkin, S.R.; Bao, Z. Tuning Crystalline Solid-State Order and Charge Transport via Building-Block Modification of Oligothiophenes. Adv. Mater. 2009, 21, 3678–3681. [Google Scholar] [CrossRef]
- Fitzner, R.; Reinold, E.; Mishra, A.C.; Men Osteritz, E.; Ziehlke, H.; Körner, C.; Leo, K.; Riede, M.K.; Weil, M.; Tsaryova, O.D.; et al. Dicyanoviny-Substituted Oligothiophenes: Structural Property Relationships and Application in Vacuu-Processed Small Molecule Organic Solar Cells. Adv. Funct. Mater. 2011, 21, 897–910. [Google Scholar] [CrossRef]
- Wang, C.; Dong, H.; Hu, W.; Liu, Y.; Zhu, D. Semiconducting π-Conjugated Systems in Field-Effect Transistors: A Material Odyssey of Organic Electronics. Chem. Rev. 2012, 112, 2208–2267. [Google Scholar] [CrossRef] [PubMed]
- Huang, W.; Xie, W.; Huang, H.; Zhang, H.; Liu, H. Designing Organic Semiconductors with Ultrasmall Reorganization Energies: Insights from Molecular Symmetry, Aromaticity and Energy Gap. J. Phys. Chem. Lett. 2020, 11, 4548–4553. [Google Scholar] [CrossRef] [PubMed]
- Fichou, D. Structural order in conjugated oligothiophenes and its implications on opto-electronic devices. J. Mater. Chem. 2000, 10, 571–588. [Google Scholar] [CrossRef]
- Costa, J.C.S.; Taveira, R.J.S.; Lima, C.F.R.A.C.; Mendes, A.; Santos, L.M.N.B.F. Optical band gaps of organic semiconductor materials. Opt. Mater. 2016, 58, 51–60. [Google Scholar] [CrossRef]
- Ju, X.-H.; Liao, X. Electronic mobilities of fluorinated oligoacenes. Int. J. Mater. Res. 2013, 104, 109–113. [Google Scholar] [CrossRef]
- Sanders, S.N.; Kumarasamy, E.; Pun, A.B.; Steigerwald, M.L.; Sfeir, M.Y.; Campos, L.M. Intramolecular Singlet Fission in Oligoacene Heterodimers. Angew. Chem. Int. Ed. 2016, 55, 3373–3377. [Google Scholar] [CrossRef]
- Zhang, F.; Wu, D.; Xu, Y.; Feng, X. Thiophene-based conjugated oligomers for organic solar cells. J. Mater. Chem. 2011, 21, 17590–17600. [Google Scholar] [CrossRef]
- Turkoglu, G.; Çinar, M.E.; Ozturk, T. Thiophene-Based Organic Semiconductors. Top. Curr. Chem. 2017, 375, 1–45. [Google Scholar] [CrossRef]
- Zade, S.S.; Bendikov, M. Cyclic Oligothiophenes: Novel Organic Materials and Models for Polythiophene. A Theoretical Study. J. Org. Chem. 2006, 71, 2972–2981. [Google Scholar] [CrossRef] [PubMed]
- Koskin, I.P.; Mostovich, E.A.; Benassi, E.; Kazantsev, M.S. Way to Highly Emissive Materials: Increase of Rigidity by Introduction of a Furan Moiety in Co-Oligomers. J. Phys. Chem. C 2017, 121, 23359–23369. [Google Scholar] [CrossRef]
- Gidron, O.; Dadvand, A.; Sun, E.W.-H.; Chung, I.J.; Shimon, L.J.W.; Bendikov, M.; Perepichka, D.F. Oligofuran-containing molecules for organic electronics. J. Mater. Chem. C 2013, 1, 4358–4367. [Google Scholar] [CrossRef]
- Gidron, O.; Bendikov, M. α-Oligofurans: An emerging class of conjugated oligomers for organic electronics. Angew. Chem. 2014, 5310, 2546–2555. [Google Scholar] [CrossRef] [PubMed]
- Sharma, S.; Bendikov, M. α-Oligofurans: A Computational Study. Chemistry 2013, 19, 13127–13139. [Google Scholar] [CrossRef]
- Zade, S.S.; Bendikov, M. Study of Hopping Transport in Long Oligothiophenes and Oligoselenophenes: Dependence of Reorganization Energy on Chain Length. Chemistry 2008, 14, 6734–6741. [Google Scholar] [CrossRef]
- Gandini, A. Polymers from Renewable Resources: A Challenge for the Future of Macromolecular Materials. Macromolecules 2008, 41, 9491–9504. [Google Scholar] [CrossRef]
- Gandini, A.; Belgacem, M.N. Chapter 6-Furan Derivatives and Furan Chemistry at the Service of Macromolecular Materials. In Monomers, Polymers and Composites from Renewable Resources; Belgacem, M.N., Gandini, A., Eds.; Elsevier: Amsterdam, The Netherlands, 2008; pp. 115–152. [Google Scholar]
- Binder, J.B.; Raines, R.T. Simple Chemical Transformation of Lignocellulosic Biomass into Furans for Fuels and Chemicals. J. Am. Chem. Soc. 2009, 131, 1979–1985. [Google Scholar] [CrossRef] [PubMed]
- Gandini, A. The irruption of polymers from renewable resources on the scene of macromolecular science and technology. Green Chem. 2011, 13, 1061–1083. [Google Scholar] [CrossRef]
- Okada, M.; Tachikawa, K.; Aoi, K. Biodegradable polymers based on renewable resources. III. copolyesters composed of 1,4:3,6-dianhydro-d-glucitol, 1,1-bis(5-carboxy-2-furyl)ethane and aliphatic dicarboxylic acid units. J. Appl. Polym. Sci. 1999, 74, 3342–3350. [Google Scholar] [CrossRef]
- Koopman, F.; Wierckx, N.; de Winde, J.H.; Ruijssenaars, H.J. Identification and characterization of the furfural and 5-(hydroxymethyl)furfural degradation pathways of Cupriavidus basilensis HMF14. Proc. Natl. Acad. Sci. USA 2010, 107, 4919–4924. [Google Scholar] [CrossRef] [Green Version]
- Gandini, A. Polymers and Oligomers Containing Furan Rings. In Agricultural and Synthetic Polymers; American Chemical Society: Washington DC, USA, 1990; Volume 433, pp. 195–208. [Google Scholar]
- Hutchison, G.R.; Ratner, M.A.; Marks, T.J. Intermolecular Charge Transfer between Heterocyclic Oligomers. Effects of Heteroatom and Molecular Packing on Hopping Transport in Organic Semiconductors. J. Am. Chem. Soc. 2005, 127, 16866–16881. [Google Scholar] [CrossRef]
- Gidron, O.; Dadvand, A.; Sheynin, Y.; Bendikov, M.; Perepichka, D.F. Towards “green” electronic materials. α-Oligofurans as semiconductors. Chem. Commun. 2011, 477, 1976–1978. [Google Scholar] [CrossRef] [PubMed]
- Seixas de Melo, J.; Elisei, F.; Gartner, C.; Aloisi, G.G.; Becker, R.S. Comprehensive Investigation of the Photophysical Behavior of Oligopolyfurans. J. Phys. Chem. A 2000, 104, 6907–6911. [Google Scholar] [CrossRef] [Green Version]
- Gidron, O.; Diskin-Posner, Y.; Bendikov, M. α-Oligofurans. J. Am. Chem. Soc. 2010, 132, 2148–2150. [Google Scholar] [CrossRef] [PubMed]
- Hättig, C.; Weigend, F. CC2 excitation energy calculations on large molecules using the resolution of the identity approximation. J. Chem. Phys. 2000, 113, 5154–5161. [Google Scholar] [CrossRef]
- Hättig, C. Geometry optimizations with the coupled-cluster model CC2 using the resolution-of-the-identity approximation. J. Chem. Phys. 2003, 118, 7751–7761. [Google Scholar] [CrossRef]
- Köhn, A.; Hättig, C. Analytic gradients for excited states in the coupled-cluster model CC2 employing the resolution-of-the-identity approximation. J. Chem. Phys. 2003, 119, 5021–5036. [Google Scholar] [CrossRef]
- Seidler, T.; Andrzejak, M.; Pawlikowski, M.T. The magnetic circular dichroism (MCD) and absorption studies of 1,8-naphthalimide. The theoretical analysis in terms of density functional (DF) and coupled cluster (CC) theories. Chem. Phys. Lett. 2013, 555, 87–91. [Google Scholar] [CrossRef]
- Andrzejak, M.; Kolek, P. Theoretical Modeling of Deuteration-Induced Shifts of the 0–0 Bands in Absorption Spectra of Selected Aromatic Amines: The Role of the Double-Well Potential. J. Phys. Chem. A 2013, 117, 12770–12782. [Google Scholar] [CrossRef] [PubMed]
- Andrzejak, M.; Orzeł, Ł. Joint theoretical and experimental study on the phosphorescence of 2,2′-bithiophene. Phys. Chem. Chem. Phys. 2014, 16, 5605–5612. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Andrzejak, M.; Szczepanik, D.W.; Orzeł, Ł. The lowest triplet states of bridged cis-2,2′-bithiophenes–theory vs. experiment. Phys. Chem. Chem. Phys. 2015, 17, 5328–5337. [Google Scholar] [CrossRef]
- Kolek, P.; Andrzejak, M.; Hakalla, R.; Szajna, W. Quantitatively Adequate Calculations of the H-Chelate Ring Distortion upon the S0 → S1(ππ*) Excitation in Internally H-Bonded o-Anthranilic Acid: CC2 Coupled-Cluster versus TDDFT. J. Phys. Chem. A 2018, 122, 6243–6255. [Google Scholar] [CrossRef]
- Kolek, P.; Andrzejak, M.; Uchacz, T.; Szlachcic, P. Consistent Franck–Condon modeling of geometry changes for the S0→S1(ππ*) excitation in anthranilic acid: LIF spectroscopy aided by CC2 or TDDFT vibrations. J. Quant. Spectrosc. Radiat. Transf. 2020, 242, 106747. [Google Scholar] [CrossRef]
- Najmidin, K.; Kerim, A.; Abdirishit, P.; Kalam, H.; Tawar, T. A comparative study of the aromaticity of pyrrole, furan, thiophene, and their aza-derivatives. J. Mol. Modeling 2013, 19, 3529–3535. [Google Scholar] [CrossRef]
- Fassioli, F.; Dinshaw, R.; Arpin, P.C.; Scholes, G.D. Photosynthetic light harvesting: Excitons and coherence. J. R. Soc. Interface 2014, 11, 20130901. [Google Scholar] [CrossRef]
- Aragó, J.; Troisi, A. Regimes of Exciton Transport in Molecular Crystals in the Presence of Dynamic Disorder. Adv. Funct. Mater. 2016, 26, 2316–2325. [Google Scholar] [CrossRef]
- Grover, M.; Silbey, R. Exciton Migration in Molecular Crystals. J. Chem. Phys. 1971, 54, 4843–4851. [Google Scholar] [CrossRef] [Green Version]
- Mori-Sánchez, P.; Cohen, A.J.; Yang, W. Many-electron self-interaction error in approximate density functionals. J. Chem. Phys. 2006, 125, 201102. [Google Scholar] [CrossRef] [PubMed]
- Cohen, A.J.; Mori-Sánchez, P.; Yang, W. Challenges for Density Functional Theory. Chem. Rev. 2012, 112, 289–320. [Google Scholar] [CrossRef] [PubMed]
- Mori-Sánchez, P.; Cohen, A.J.; Yang, W. Localization and Delocalization Errors in Density Functional Theory and Implications for Band-Gap Prediction. Phys. Rev. Lett. 2008, 100, 146401. [Google Scholar] [CrossRef] [Green Version]
- Yang, S.; Kertesz, M. Bond Length Alternation and Energy Band Gap of Polyyne. J. Phys. Chem. A 2006, 110, 9771–9774. [Google Scholar] [CrossRef]
- Zerbi, G. Vibrational Spectroscopy of Conducting Polymers: Theory and Perspective. In Handbook of Vibrational Spectroscopy; John Wiley & Sons, Ltd.: New York, NY, USA, 2007. [Google Scholar]
- Lucotti, A.; Tommasini, M.; Zoppo, M.D.; Castiglioni, C.; Zerbi, G.; Cataldo, F.; Casari, C.S.; Bassi, A.L.; Russo, V.; Bogana, M.; et al. Raman and SERS investigation of isolated sp carbon chains. Chem. Phys. Lett. 2006, 417, 78–82. [Google Scholar] [CrossRef]
- Milani, A.; Tommasini, M.; Del Zoppo, M.; Castiglioni, C.; Zerbi, G. Carbon nanowires: Phonon and π-electron confinement. Phys. Rev. B 2006, 74, 153418. [Google Scholar] [CrossRef]
- Tommasini, M.; Fazzi, D.; Milani, A.; Del Zoppo, M.; Castiglioni, C.; Zerbi, G. Intramolecular Vibrational Force Fields for Linear Carbon Chains through an Adaptative Linear Scaling Scheme. J. Phys. Chem. A 2007, 111, 11645–11651. [Google Scholar] [CrossRef]
- Chou, C.-P.; Li, W.-F.; Witek, H.A.; Andrzejak, M. Vibrational Spectroscopy of Linear Carbon Chains. In Spectroscopy, Dynamics and Molecular Theory of Carbon Plasmas and Vapors; World Scientific Publishing Co.: Singapore, 2011; pp. 375–415. [Google Scholar]
- Abdurahman, A.; Shukla, A.; Dolg, M. Ab initio many-body calculations on infinite carbon and boron-nitrogen chains. Phys. Rev. B 2002, 65, 115106. [Google Scholar] [CrossRef] [Green Version]
- Zeinalipour-Yazdi, C.D.; Pullman, D.P. Quantitative Structure−Property Relationships for Longitudinal, Transverse, and Molecular Static Polarizabilities in Polyynes. J. Phys. Chem. B 2008, 112, 7377–7386. [Google Scholar] [CrossRef]
- Chalifoux, W.A.; McDonald, R.; Ferguson, M.J.; Tykwinski, R.R. tert-Butyl-End-Capped Polyynes: Crystallographic Evidence of Reduced Bond-Length Alternation. Angew. Chem. Int. Ed. 2009, 48, 7915–7919. [Google Scholar] [CrossRef]
- Reimers, J.R. A practical method for the use of curvilinear coordinates in calculations of normal-mode-projected displacements and Duschinsky rotation matrices for large molecules. J. Chem. Phys. 2001, 115, 9103–9109. [Google Scholar] [CrossRef]
- Gozem, S.; Krylov, A.I. The ezSpectra Suite: An Easy-to-Use Toolkit for Spectroscopy Modeling. Available online: https://wires.onlinelibrary.wiley.com/doi/abs/10.1002/wcms.1546 (accessed on 10 September 2021).
- Becke, A.D. Density-functional exchange-energy approximation with correct asymptotic behavior. Phys. Rev. A 1988, 38, 3098–3100. [Google Scholar] [CrossRef]
- Perdew, J.P. Density-functional approximation for the correlation energy of the inhomogeneous electron gas. Phys. Rev. B 1986, 33, 8822–8824. [Google Scholar] [CrossRef]
- Tao, J.; Perdew, J.P.; Staroverov, V.N.; Scuseria, G.E. Climbing the Density Functional Ladder: Nonempirical Meta—Generalized Gradient Approximation Designed for Molecules and Solids. Phys. Rev. Lett. 2003, 91, 146401. [Google Scholar] [CrossRef] [Green Version]
- Staroverov, V.N.; Scuseria, G.E.; Tao, J.; Perdew, J.P. Comparative assessment of a new nonempirical density functional: Molecules and hydrogen-bonded complexes. J. Chem. Phys. 2003, 119, 12129–12137. [Google Scholar] [CrossRef]
- Becke, A.D. Density-functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 1993, 98, 5648–5652. [Google Scholar] [CrossRef] [Green Version]
- Lee, C.; Yang, W.; Parr, R.G. Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys. Rev. B 1988, 37, 785–789. [Google Scholar] [CrossRef] [Green Version]
- Miehlich, B.; Savin, A.; Stoll, H.; Preuss, H. Results obtained with the correlation energy density functionals of becke and Lee, Yang and Parr. Chem. Phys. Lett. 1989, 157, 200–206. [Google Scholar] [CrossRef]
- Adamo, C.; Barone, V. Toward reliable density functional methods without adjustable parameters: The PBE0 model. J. Chem. Phys. 1999, 110, 6158–6170. [Google Scholar] [CrossRef]
- Yu, H.S.; He, X.; Li, S.L.; Truhlar, D.G. MN15: A Kohn–Sham global-hybrid exchange–correlation density functional with broad accuracy for multi-reference and single-reference systems and noncovalent interactions. Chem. Sci. 2016, 7, 5032–5051. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Becke, A.D. A new mixing of Hartree–Fock and local density-functional theories. J. Chem. Phys. 1993, 98, 1372–1377. [Google Scholar] [CrossRef]
- Yanai, T.; Tew, D.P.; Handy, N.C. A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP). Chem. Phys. Lett. 2004, 393, 51–57. [Google Scholar] [CrossRef] [Green Version]
- Okuno, K.; Shigeta, Y.; Kishi, R.; Miyasaka, H.; Nakano, M. Tuned CAM-B3LYP functional in the time-dependent density functional theory scheme for excitation energies and properties of diarylethene derivatives. J. Photochem. Photobiol. A 2012, 235, 29–34. [Google Scholar] [CrossRef]
- Chai, J.-D.; Head-Gordon, M. Systematic optimization of long-range corrected hybrid density functionals. J. Chem. Phys. 2008, 128, 084106. [Google Scholar] [CrossRef] [PubMed]
- Andrzejak, M.; Petelenz, P. Vibronic relaxation energies of acene-related molecules upon excitation or ionization. Phys. Chem. Chem. Phys. 2018, 20, 14061–14071. [Google Scholar] [CrossRef]
- Schreiber, M.; Silva-Junior, M.R.; Sauer, S.P.A.; Thiel, W. Benchmarks for electronically excited states: CASPT2, CC2, CCSD, and CC3. J. Chem. Phys. 2008, 128, 134110. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Balasubramani, S.G.; Chen, G.P.; Coriani, S.; Diedenhofen, M.; Frank, M.S.; Franzke, Y.J.; Furche, F.; Grotjahn, R.; Harding, M.E.; Hättig, C.; et al. TURBOMOLE: Modular program suite for ab initio quantum-chemical and condensed-matter simulations. J. Chem. Phys. 2020, 152, 184107. [Google Scholar] [CrossRef]
- Frisch, M.J.; Trucks, G.W.; Schlegel, H.B.; Scuseria, G.E.; Robb, M.A.; Cheeseman, J.R.; Scalmani, G.; Barone, V.; Petersson, G.A.; Nakatsuji, H.; et al. Supporting Information for Rotational Spectroscopic Studies of C–H...F Interactions in the Vinyl Fluoride...Difluoromethane Complex. Available online: https://s3-eu-west-1.amazonaws.com (accessed on 10 September 2021).
- Witkowski, A.; Moffitt, W. Electronic Spectra of Dimers: Derivation of the Fundamental Vibronic Equation. J. Chem. Phys. 1960, 33, 872–875. [Google Scholar] [CrossRef]
- Zade, S.S.; Zamoshchik, N.; Bendikov, M. From Short Conjugated Oligomers to Conjugated Polymers. Lessons from Studies on Long Conjugated Oligomers. Acc. Chem. Res. 2011, 44, 14–24. [Google Scholar] [CrossRef]
- Li, W.-F.; Andrzejak, M.; Witek, H.A. Evolution of physical properties of conjugated systems. Phys. Status Solidi (b) 2012, 249, 306–316. [Google Scholar] [CrossRef]
- Ma, J.; Li, S.; Jiang, Y. A Time-Dependent DFT Study on Band Gaps and Effective Conjugation Lengths of Polyacetylene, Polyphenylene, Polypentafulvene, Polycyclopentadiene, Polypyrrole, Polyfuran, Polysilole, Polyphosphole, and Polythiophene. Macromolecules 2002, 35, 1109–1115. [Google Scholar] [CrossRef]
- Hutchison, G.R.; Zhao, Y.-J.; Delley, B.; Freeman, A.J.; Ratner, M.A.; Marks, T.J. Electronic structure of conducting polymers: Limitations of oligomer extrapolation approximations and effects of heteroatoms. Phys. Rev. B 2003, 68, 035204. [Google Scholar] [CrossRef]
- Zade, S.S.; Bendikov, M. From Oligomers to Polymer: Convergence in the HOMO−LUMO Gaps of Conjugated Oligomers. Org. Lett. 2006, 8, 5243–5246. [Google Scholar] [CrossRef] [PubMed]
- Salzner, U.; Aydin, A. Improved Prediction of Properties of π-Conjugated Oligomers with Range-Separated Hybrid Density Functionals. J. Chem. Theory Comput. 2011, 7, 2568–2583. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Ferrón, C.C.; Delgado, M.C.R.; Gidron, O.; Sharma, S.; Sheberla, D.; Sheynin, Y.; Bendikov, M.; Navarrete, J.T.L.; Hernández, V. α-Oligofurans show a sizeable extent of π-conjugation as probed by Raman spectroscopy. Chem. Commun. 2012, 48, 6732–6734. [Google Scholar] [CrossRef]
- Fulton, R.L.; Gouterman, M. Vibronic Coupling. I. Mathematical Treatment for Two Electronic States. J. Chem. Phys. 1961, 35, 1059–1071. [Google Scholar] [CrossRef]
- Ditchburn, R.W.; O’Neill, E.L. Light, 3rd ed.; Available online: https://aapt.scitation.org/doi/10.1119/1.10935 (accessed on 10 September 2021).
- Friese, D.H.; Törk, L.; Hättig, C. Vibrational frequency scaling factors for correlation consistent basis sets and the methods CC2 and MP2 and their spin-scaled SCS and SOS variants. J. Chem. Phys. 2014, 141, 194106. [Google Scholar] [CrossRef]
- Kanchanakungwankul, S.B.J.L.; Zheng, J.; Alecu, I.M.; Lynch, B.J.; Zhao, Y.; Truhlar, D.G. Database of Frequency Scale Factors for Electronic Model Chemistries. Available online: https://comp.chem.umn.edu/freqscale/190107_Database_of_Freq_Scale_Factors_v4.pdf (accessed on 10 September 2021).
2O | 3O | 4O | 5O | 6O | 7O | 8O | 9O | |
---|---|---|---|---|---|---|---|---|
BP | 4.165 | 3.298 | 2.802 | 2.475 | 2.242 | 2.070 | 1.938 | 1.835 |
TPSSh | 4.380 | 3.531 | 3.055 | 2.748 | 2.536 | 2.391 | 2.276 | 2.188 |
B3LYP | 4.418 | 3.604 | 3.154 | 2.870 | 2.677 | 2.539 | 2.439 | 2.363 |
PBE0 | 4.541 | 3.727 | 3.282 | 3.003 | 2.815 | 2.683 | 2.586 | 2.513 |
MN15 | 4.593 | 3.847 | 3.449 | 3.208 | 3.050 | 2.941 | 2.855 | 2.803 |
BHLYP | 4.771 | 4.020 | 3.621 | 3.380 | 3.223 | 3.114 | 3.036 | 2.978 |
CAM-B3LYP | 4.720 | 3.998 | 3.621 | 3.396 | 3.250 | 3.149 | 3.078 | 3.023 |
tuned CAM-B3LYP | 4.456 | 3.715 | 3.329 | 3.097 | 2.946 | 2.842 | 2.767 | 2.709 |
ωB97X | 4.864 | 4.198 | 3.859 | 3.660 | 3.533 | 3.446 | 3.385 | 3.338 |
CC2 | 4.906 | 4.137 | 3.720 | 3.457 | 3.300 | 3.186 | 3.105 | 3.045 |
Experiment 1 | 4.531 | 3.896 | 3.556 | 3.345 | 3.219 | 3.123 | 3.081 | 3.033 |
2O | 3O | 4O | 5O | 6O | 7O | 8O | 9O | |
---|---|---|---|---|---|---|---|---|
BP | 3.773 | 3.043 | 2.612 | 2.315 | 2.096 | 1.929 | 1.799 | 1.697 |
TPSSh | 3.902 | 3.185 | 2.770 | 2.492 | 2.292 | 2.144 | 2.031 | 1.944 |
B3LYP | 3.873 | 3.181 | 2.787 | 2.528 | 2.346 | 2.213 | 2.115 | 2.042 |
PBE0 | 3.971 | 3.274 | 2.882 | 2.626 | 2.449 | 2.323 | 2.231 | 2.163 |
MN15 | 3.923 | 3.277 | 2.924 | 2.703 | 2.557 | 2.460 | 2.393 | 2.347 |
BHLYP | 4.015 | 3.360 | 3.003 | 2.782 | 2.640 | 2.545 | 2.482 | 2.440 |
CAM-B3LYP | 3.990 | 3.357 | 3.017 | 2.813 | 2.684 | 2.601 | 2.547 | 2.513 |
tuned CAM-B3LYP | 3.881 | 3.228 | 2.878 | 2.663 | 2.524 | 2.431 | 2.368 | 2.325 |
ωB97X | 4.041 | 3.452 | 3.150 | 2.981 | 2.882 | 2.826 | 2.793 | 2.775 |
CC2 1 | 4.262 | 3.584 | 3.193 | 2.942 | 2.775 | 2.663 | ||
Experiment 2 | 3.953 | 3.370 | 3.065 | 2.847 | 2.727 | 2.658 | 2.610 | 2.583 |
2O | 3O | 4O | 5O | 6O | 7O | 8O | 9O | |
---|---|---|---|---|---|---|---|---|
BP | 0.196 | 0.128 | 0.095 | 0.080 | 0.073 | 0.070 | 0.069 | 0.069 |
TPSSh | 0.239 | 0.173 | 0.142 | 0.128 | 0.122 | 0.124 | 0.122 | 0.122 |
B3LYP | 0.273 | 0.211 | 0.184 | 0.171 | 0.166 | 0.163 | 0.162 | 0.160 |
PBE0 | 0.285 | 0.226 | 0.200 | 0.188 | 0.183 | 0.180 | 0.178 | 0.175 |
MN15 | 0.335 | 0.285 | 0.263 | 0.253 | 0.246 | 0.241 | 0.231 | 0.228 |
BHLYP | 0.378 | 0.330 | 0.309 | 0.299 | 0.292 | 0.284 | 0.277 | 0.269 |
CAM-B3LYP | 0.365 | 0.321 | 0.302 | 0.291 | 0.283 | 0.274 | 0.265 | 0.255 |
tuned CAM-B3LYP | 0.287 | 0.243 | 0.225 | 0.217 | 0.211 | 0.205 | 0.199 | 0.192 |
ωB97X | 0.411 | 0.373 | 0.354 | 0.340 | 0.325 | 0.310 | 0.296 | 0.282 |
CC2 1 | 0.322 | 0.277 | 0.264 | 0.258 | 0.263 | 0.262 | ||
Experiment 2 | 0.297 | 0.274 | 0.260 | 0.249 | 0.246 | 0.233 | 0.236 | 0.225 |
Absorption | Emission | Reorganization | ||||
---|---|---|---|---|---|---|
Slope | Intercept | Slope | Intercept | Slope | Intercept | |
BP | 6.019 | 1.227 | 5.351 | 1.185 | 0.334 | 0.021 |
TPSSh | 5.67 | 1.592 | 5.06 | 1.438 | 0.305 | 0.078 |
B3LYP | 5.325 | 1.791 | 4.745 | 1.551 | 0.290 | 0.12 |
PBE0 | 5.255 | 1.942 | 4.692 | 1.667 | 0.281 | 0.138 |
MN15 | 4.646 | 2.456 | 4.113 | 1.969 | 0.267 | 0.199 |
BHLYP | 4.644 | 2.282 | 4.11 | 1.883 | 0.267 | 0.244 |
CAM-B3LYP | 4.392 | 2.525 | 3.862 | 2.057 | 0.265 | 0.234 |
tuned CAM-B3LYP | 4.517 | 2.2 | 4.055 | 1.86 | 0.231 | 0.17 |
ωB97X | 3.945 | 2.883 | 3.32 | 2.353 | 0.313 | 0.265 |
CC2 | 4.832 | 2.502 | 4.526 | 2.032 | 0.171 | 0.229 |
Experiment 1 | 3.904 | 2.581 | 3.610 | 2.171 | 0.176 | 0.202 |
2O | 3O | 4O | |||||||||
---|---|---|---|---|---|---|---|---|---|---|---|
Absorption | Emission | Absorption | Emission | Absorption | Emission | ||||||
383 | 0.099 | 388 | 0.104 | 421 | 0.114 | 418 | 0.136 | 408 | 0.169 | 405 | 0.189 |
816 | 0.236 | 876 | 0.012 | 895 | 0.430 | 948 | 0.386 | 888 | 0.057 | 943 | 0.040 |
853 | 0.463 | 930 | 0.712 | 1030 | 0.125 | 1021 | 0.211 | 915 | 0.280 | 959 | 0.258 |
1020 | 0.193 | 1021 | 0.187 | 1033 | 0.128 | 1021 | 0.202 | ||||
1193 | 0.037 | 1174 | 0.099 | 1314 | 0.017 | 1184 | 0.023 | 1347 | 0.036 | 1187 | 0.008 |
1308 | 0.023 | 1333 | 0.025 | 1363 | 0.026 | 1335 | 0.064 | 1392 | 0.017 | 1337 | 0.089 |
1447 | 0.018 | 1431 | 0.062 | 1435 | 0.020 | 1425 | 0.017 | 1488 | 0.038 | 1487 | 0.010 |
1492 | 0.092 | 1537 | 0.183 | 1516 | 0.057 | 1545 | 0.092 | 1519 | 0.037 | 1547 | 0.057 |
1776 | 0.873 | 1687 | 0.688 | 1759 | 0.867 | 1672 | 0.700 | 1660 | 0.063 | 1660 | 0.712 |
1751 | 0.780 |
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations. |
© 2021 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
Share and Cite
Filipowska, K.; Pawlikowski, M.T.; Andrzejak, M. Optical Spectra of Oligofurans: A Theoretical Approach to the Transition Energies, Reorganization Energies, and the Vibronic Activity. Molecules 2021, 26, 7163. https://doi.org/10.3390/molecules26237163
Filipowska K, Pawlikowski MT, Andrzejak M. Optical Spectra of Oligofurans: A Theoretical Approach to the Transition Energies, Reorganization Energies, and the Vibronic Activity. Molecules. 2021; 26(23):7163. https://doi.org/10.3390/molecules26237163
Chicago/Turabian StyleFilipowska, Karolina, Marek T. Pawlikowski, and Marcin Andrzejak. 2021. "Optical Spectra of Oligofurans: A Theoretical Approach to the Transition Energies, Reorganization Energies, and the Vibronic Activity" Molecules 26, no. 23: 7163. https://doi.org/10.3390/molecules26237163