Electronic Structure of Thienylene Vinylene Oligomers:  Singlet Excited States, Triplet Excited States, Cations, and Dications

• Published in: The journal of physical chemistry. B 2004-10, Vol.108 (41), p.16139-16146
• Main Authors: Grozema, F. C, van Duijnen, P. Th, Siebbeles, L. D. A, Goossens, A, de Leeuw, S. W
• Format: Article
• Language: English
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/jp048445n

This paper describes a quantum chemical study of the electronic structure of thienylene vinylene oligomers ranging in size from two thienylene rings (2TV) to 12TV. The geometries of the TV oligomers in the ground state, the lowest triplet state, and the singly and doubly oxidized states were optimized using density functional theory calculations. The electronic absorption spectra were obtained from configuration interaction calculations with an INDO/s reference wave function. Comparison with experimental data shows that the agreement is satisfactory, except for the triplet−triplet absorption spectra. For closed shell systems (ground state and doubly occupied state), the spectra were also calculated by time dependent density functional theory (TDDFT). TDDFT considerably underestimates the neutral singlet−singlet excitation energies for longer chains. The nature of the excited states for the TV radical cations was found to be more similar to that of thiophenes than to that of phenylene vinylenes, indicating that the sulfur atom has a marked influence on the π-electron system. For the (singlet) absorption spectra of doubly oxidized TVs, the results from TDDFT calculations are surprisingly good; they are also good for long chains. TDDFT calculations for doubly charged TVs also confirm the existence of a second, weak absorption band as has been found experimentally.