Journal of Physical Chemistry, Vol.99, No.25, 10196-10200, 1995
Shorter Bipolarons in Oligo(P-Phenyls) and in Poly(P-Phenylene) - An Ab-Initio SCF Study
The structures and energies of neutral benzenoid and neutral quinonoid oligo(p-phenyls) and of oligo(p-phenyl) dications and dianions were calculated at the ab initio SCF level for oligomers containing up to 11 rings. Compared to analogous theoretical data as obtained earlier on oligathiophenes, we compute a spatial extension of the positive and negative bipolaronic defects in poly(p-phenylene) of only about three rings, thus considerably shorter than in polythiophene. The shorter defect extension in poly(p-phenylene) correlates also with the finding that even if one attempts to force the quinonoid structure by the addition of appropriate terminal groups, a transition to the aromatic benzenoid structure occurs already in the center of chains as short as about six rings.
Keywords:POLY-P-PHENYLENE;ELECTRONIC-STRUCTURE;DOPED POLYPARAPHENYLENE;CONDUCTING POLYMERS;CONJUGATED POLYMERS;BASIS-SETS;POLYACETYLENE;POLARONS;POLY(PARA-PHENYLENE);OLIGOMERS