A Time-Dependent DFT Study on Band Gaps and Effective Conjugation Lengths of Polyacetylene, Polyphenylene, Polypentafulvene, Polycyclopentadiene, Polypyrrole, Polyfuran, Polysilole, Polyphosphole, and Polythiophene

• DOI: 10.1021/ma011279m
• Publication Date: 2002-07-26T04:45:58Z
• Authors: Jing Ma; Shuhua Li; Yuansheng Jiang
• Keywords: 02 engineering and technology; 0210 nano-technology; 01 natural sciences; 0104 chemical sciences

The chain length dependence of excitation energies of oilgomers of polyene, p-phenylene, pentafulvene, cyclopentadiene, pyrrole, furan, silole, phosphole, and thiophene was studied employing the time-dependent density functional theory with B3LYP functional. Band gaps and effective conjugation lengths of the corresponding polymers were obtained by extrapolating vertical excitation energies of trimers through pentamers to infinite chain length. Polypentafulvene, polycyclopentadiene, polysilole, and polyphosphole were predicted to have smaller band gaps than polythiophene, and polypentafulvene has the smallest band gap. Among the studied cyclopentadiene-based polymers, those with the third row heteroatoms were found to have narrower band gaps than their second row counterparts.