Abstract
Ground state and excitation energies of poly(3-methoxy-thio-phene) (PMT) and poly(thienylene vinylene) (PTV) conjugated polymers are studied by first principles density functional theory (DFT). Two basic approaches of computational chemistry and physics are compared: time dependent DFT (TDDFT) of clusters and ab initio pseudopotentials within a standard DFT (PP-DFT) of infinite polymer chains. We demonstrate that series of excitation energies of PMT calculated by TDDFT with increased unit numbers converge well to the real experimentally measured energy gaps. Combination of TDDFT cluster method with PP-DFT approach for infinite chain provides single-gap quasiparticle correction value needed for optical calculations. Infinite chain model is used to calculate optical absorption of PTV.
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Dhanabalan, A., van Duren, J.K.J., van Hal, P.A., van Dongen, J.L.J., Janssen, R.A.J.: Synthesis and characterization of a low bandgap conjugated polymer for bulk heterojunction photovoltaic cells. Adv. Funct. Mater. 11, 255–262 (2001)
Sun, S.S., Sariciftci, N.S.: Organic Photovoltaics: Mechanisms, Materials, and Devices. CRC Press, Boca Raton (2005)
Patil, A.O., Heeger, A.J., Wudl, F.: Optical properties of conducting polymers. Chem. Rev. 88, 183–200 (1988)
Skotheim, T.A. (ed.): Handbook of Conducting Polymers, 2nd edn. CRC Press, Boca Raton (1997)
Eckhardt, H., Shacklette, L.W., Jen, K.Y., Elsenbaumer, R.L.: The electronic and electrochemical properties of poly(phenylene vinylenes) and poly(thienylene vinylenes): An experimental and theoretical study. J. Chem. Phys. 91, 1303–1315 (1989)
Blohm, M.L., Pickett, J.E., Van Dort, P.C.: Synthesis, characterization, and stability of poly(3,4-dibutoxythiophenevinylene) copolymers. Macromol. 26, 2704–2710 (1993)
Toussaint, J.M., Bredas, J.L.: Theoretical analysis of the geometric and electronic structure of small-band-gap polythiophenes: poly(5,5’-bithiophene methine) and its derivatives. Macromol. 26, 5240–5248 (1993)
Ortmann, F., Schmidt, W.G., Bechstedt, F.: Attracted by long-range electron correlation: Adenine on graphite. Phys. Rev. Lett. 95, 186101–186105 (2005)
Gavrilenko, V.I.: Ab initio modeling of optical properties of organic molecules and molecular complexes. In: Alexandrov, V.N., van Albada, G.D., Sloot, P.M.A., Dongarra, J. (eds.) ICCS 2006. LNCS, vol. 3993, pp. 89–96. Springer, Heidelberg (2006)
Rohlfing, M., Tiago, M.L., Louie, S.G.: First-principles calculation of optical absorption spectra in conjugated polymers: role of electron-hole interaction. Synth. Met. 116, 101 (2001)
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. Macromol. 35, 1109–1115 (2002)
Kohn, W., Becke, A.D., Parr, R.G.: Density functional theory of electronic structure. J. Phys. Chem. 100, 12974–12980 (1996)
Perdew, J.P., Wang, Y.: Accurate and simple analytic representation of the electron-gas correlation energy. Phys. Rev. B 45, 13244–13249 (1992)
Perdew, J.P., Burke, K., Ernzerhof, M.: Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996)
Miller, W.H., Hernandez, R., Handy, N.C., Jayatilaka, D., Willets, A.: Ab initio calculation of anharmonic constants for a transition state, with application to semiclassical transition state tunneling probabilities. Chem. Phys. Lett. 172, 62 (1990)
Delley, B.: An all-electron numerical method for solving the local density functional for polyatomic molecules. J. Chem. Phys. 92, 508–517 (1990)
Delley, B.: From molecules to solids with the DMol3 approach. J. Chem. Phys. 113, 7756–7764 (2000)
Segall, M.D., Lindan, P.J.D., Probert, M.J., Pickard, C.J., Hasnip, P.J., Clark, S.J., Payne, M.C.: First-principles simulation: ideas, illustrations and the CASTEP code. J. Phys.Cond. Matt. 14, 2717–2744 (2002)
Gavrilenko, A.V., Matos, T., Bonner, C.E., Sun, S.S., Zhang, C., Gavrilenko, V.I.: Optical absorption of poly(thiophene vinylene) conjugated polymers. Experiment and first principle theory. J. Phys. Chem. B (in press) (2008)
Gavrilenko, V.I., Bechstedt, F.: Optical functions of semiconductors beyond density-functional theory and random-phase approximation. Phys. Rev. B 55, 4343–4352 (1997)
Bonner, C.E., Charter, S., Lorts, A., Adebolu, O.I., Zhang, C., Sun, S.S., Gavrilenko, V.I.: Luminescence and optical absorption of conjugated poly-phenylene-vinylene polymers. In: Proc. of SPIE, vol. 6320, 63200J (2006)
Seo, K., Choi, S., Zhang, C., Sun, S.S., Bonner, C.: Processing and molecular packing of a derivatized PPV -donor-bridge-acceptor-bridge- type block copolymer for potential photovoltaic applications. Adv. Mater (in press) (2008)
Onida, G., Reining, L., Rubio, A.: Electronic excitations: density-functional versus many-body Green’s-function approaches. Rev. Mod. Phys. 74, 601–633 (2002)
Matos, T.D.: Design, synthesis, and characterization of 3-dodedyl-2,5-poly(thie-nylene vinylene) polymer for optoelectronics and solar energy conversions. Master’s thesis, Norfolk State University (2007)
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Gavrilenko, A.V., Black, S.M., Sykes, A.C., Bonner, C.E., Gavrilenko, V.I. (2008). Computations of Ground State and Excitation Energies of Poly(3-methoxy-thiophene) and Poly(thienylene vinylene) from First Principles. In: Bubak, M., van Albada, G.D., Dongarra, J., Sloot, P.M.A. (eds) Computational Science – ICCS 2008. ICCS 2008. Lecture Notes in Computer Science, vol 5102. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-540-69387-1_44
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DOI: https://doi.org/10.1007/978-3-540-69387-1_44
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