Anomalous failure of configuration interaction—Singles (CIS) method in the computation of the electronic states of N,N′-bis(4′-aminophenyl)-1,4-quinonenediimine

✍ Scribed by Lawrence T. Sein Jr.,; Yen Wei; Thanh Duong; Mark D. Kemmerer; Susan A. Jansen

• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: English
• Weight: 614 KB
• Volume: 75
• Category: Article
• ISSN: 0020-7608
• DOI: 10.1002/(sici)1097-461x(1999)75:4/5<623::aid-qua28>3.0.co;2-p

✦ Synopsis

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.

Ž . 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. ᮊ 1999