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Anomalous failure of configuration interaction—Singles (CIS) method in the computation of the electronic states of N , N ′‐bis(4′‐aminophenyl)‐1,4‐quinonenediimine
Author(s) -
Sein Lawrence T.,
Wei Yen,
Duong Thanh,
Kemmerer Mark D.,
Jansen Susan A.
Publication year - 1999
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1999)75:4/5<623::aid-qua28>3.0.co;2-p
Subject(s) - trimer , aniline , chemistry , electronic structure , ab initio , polyaniline , computational chemistry , configuration interaction , molecular orbital , redox , amine gas treating , chromophore , molecular electronic transition , oligomer , photochemistry , polymer chemistry , dimer , organic chemistry , molecule , polymerization , polymer
Ab initio molecular orbital calculations on various redox forms of the title compound, an amine‐capped trimer of aniline, have been used to characterize the electronic states responsible for the electronic spectra and observed redox chemistries. These data are important for understanding the electronic structure and application chemistry of aniline‐based materials, including the oligomeric structures and polyaniline. Calculations using configuration interaction with single substitutions (CIS)are in poor agreement with experiment. Transition energies computed using Becke's three‐parameter hybrid functional compare well with those observed in the visible and ultraviolet spectra of multiple redox forms of the title compound. The high accuracy of these calculations and correspondence between states of the amine‐capped trimer and polyaniline suggest that the electronic chromophore of polyaniline may be a small aniline oligomer. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 75: 623–629, 1999