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Through versus Cross Electron Delocalization in Polytriacetylene Oligomers: A Computational Analysis
Author(s) -
Bruschi Maurizio,
Giuffreda Maria Grazia,
Lüthi Hans Peter
Publication year - 2005
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200400202
Subject(s) - delocalized electron , chemistry , conjugated system , oligomer , trimer , density functional theory , bond length , molecular orbital , electron affinity (data page) , photochemistry , computational chemistry , crystallography , molecule , polymer , organic chemistry , dimer , crystal structure
Herein, we report a systematic theoretical investigation of the molecular and electronic properties of unsubstituted polytriacetylene (PTA) and iso ‐polytriacetylene ( iso ‐PTA) oligomers, which are characterized by through and cross π ‐conjugation pathways, respectively. The goal of the study is to compare through versus cross conjugation on the basis of the computed molecular geometries of the neutral, anionic, and cationic species, the electron affinities, ionization potentials, excitation energies, and nonlinear optical properties for oligomers up to the nonamer. Differences in the effective conjugation length are directly related to electron delocalization in cross ‐ and through ‐conjugated pathways. As in the through ‐conjugated oligomers, that is, the PTAs, the frontier orbitals of the iso ‐PTA oligomers are delocalized along the entire carbon backbone, suggesting that π‐delocalization can extend through cross‐linked carbon atoms. However, in contrast to the PTA oligomers, the bond lengths remain strictly constant and the reduction of the energy gap beyond the trimer is completely due to the correlation contribution. On the other hand, in the anions and cations, the bond lengths do change significantly with increasing chain length. Therefore, oxidation or reduction of the iso ‐PTA oligomer appears to switch on delocalization through cross‐linked carbon atoms. Obviously, the effective conjugation length is specific and depends on the observable considered.