Density functional crystal orbital study of cyano-substituted poly(para-Phenylene-Vinylene) and poly(Quinoxaline-Vinylene)

F. Bartha, I. A. Howard, P. Geerlings, C. Van Alsenoy, D. Vanderzande, T. J. Cleij, F. Bogár

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

We have calculated the optical and electronic properties of several conjugated organic polymers: poly(p-phenylene-vinylene) (PPV) and its derivatives. Cyano substitutions on the phenylene ring: poly(2,5-dicyano-p- phenylene-vinylene) (2,5-DCN-PPV) and on the vinylene linkage: poly(p-phenylene-7(,8)-(di)cyano-vinylene) are considered. In addition, poly(quinoxaline-vinylene) (PQV) is studied. The infinite isolated quasi-1D chains are treated with periodic boundary conditions, using atomic basis sets. In a comparative study of PPV, some issues regarding the selection of the functionals and basis sets are discussed and excitation energies derived from time-dependent and from ordinary methods are compared. It is concluded that for these polymers the calculations are informative at the B3LYP/6-31G** density functional theory (DFT) level. The absolute values might change with improved methods, but the similarity of the polymers suggests that the relative characterization is adequate. Band structures are communicated along with characteristics of the highest occupied and the lowest unoccupied crystal orbitals (HOCO and LUCO). Electron affinities, ionization potentials, valence and conduction bandwidths, and effective masses at the bandgap are given.

Original languageEnglish
Pages (from-to)1912-1923
Number of pages12
JournalInternational Journal of Quantum Chemistry
Volume106
Issue number8
DOIs
Publication statusPublished - Jul 2006

Fingerprint

quinoxalines
Quinoxalines
Polymers
orbitals
Electron affinity
Crystals
Organic polymers
Ionization potential
Excitation energy
Conjugated polymers
polymers
Electronic properties
Band structure
crystals
Density functional theory
Energy gap
Substitution reactions
Optical properties
Boundary conditions
electron affinity

Keywords

  • Band structure
  • Conducting polymers
  • Electron affinity
  • Ionization potential
  • PPV

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Density functional crystal orbital study of cyano-substituted poly(para-Phenylene-Vinylene) and poly(Quinoxaline-Vinylene). / Bartha, F.; Howard, I. A.; Geerlings, P.; Van Alsenoy, C.; Vanderzande, D.; Cleij, T. J.; Bogár, F.

In: International Journal of Quantum Chemistry, Vol. 106, No. 8, 07.2006, p. 1912-1923.

Research output: Contribution to journalArticle

Bartha, F. ; Howard, I. A. ; Geerlings, P. ; Van Alsenoy, C. ; Vanderzande, D. ; Cleij, T. J. ; Bogár, F. / Density functional crystal orbital study of cyano-substituted poly(para-Phenylene-Vinylene) and poly(Quinoxaline-Vinylene). In: International Journal of Quantum Chemistry. 2006 ; Vol. 106, No. 8. pp. 1912-1923.
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AB - We have calculated the optical and electronic properties of several conjugated organic polymers: poly(p-phenylene-vinylene) (PPV) and its derivatives. Cyano substitutions on the phenylene ring: poly(2,5-dicyano-p- phenylene-vinylene) (2,5-DCN-PPV) and on the vinylene linkage: poly(p-phenylene-7(,8)-(di)cyano-vinylene) are considered. In addition, poly(quinoxaline-vinylene) (PQV) is studied. The infinite isolated quasi-1D chains are treated with periodic boundary conditions, using atomic basis sets. In a comparative study of PPV, some issues regarding the selection of the functionals and basis sets are discussed and excitation energies derived from time-dependent and from ordinary methods are compared. It is concluded that for these polymers the calculations are informative at the B3LYP/6-31G** density functional theory (DFT) level. The absolute values might change with improved methods, but the similarity of the polymers suggests that the relative characterization is adequate. Band structures are communicated along with characteristics of the highest occupied and the lowest unoccupied crystal orbitals (HOCO and LUCO). Electron affinities, ionization potentials, valence and conduction bandwidths, and effective masses at the bandgap are given.

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