title: Theoretical investigation of the molecular structures and excitation spectra of triphenylamine and its derivatives.
abstract: The molecular geometries, electronic structures, and excitation energies of NPh(3), NPh(2)Me, NPhMe(2), and NMe(3), were investigated using DFT and post-Hartree Fock methods. When the structural stabilities of these compounds were compared to results obtained by using MP4(SDQ) method, it was confirmed that the optimized geometries by using MP2 method were sufficiently reliable. The excited states with large oscillator strengths consisted of transition components from the HOMO. It should be noted that the orbitals of the nitrogen atom mix with the π-orbital of the phenyl group in an anti-bonding way in the HOMO, and the orbital energy increases with this mixing. The unoccupied orbitals are generated from bonding and anti-bonding type interactions between the π-orbitals of the phenyl groups; therefore, the number of phenyl groups strongly affects the energy diagram of the compounds studied. The differences in the energy diagram cause a spectral change in these compounds in the ultraviolet region.
authors.affiliation: Division of Materials Science and Engineering, Graduate School of Science and Engineering, Yamaguchi University, 2-16-1 Tokiwadai, Ube 755-8611, Japan. sumimoto@yamaguchi-u.ac.jp
authors.forename: Michinori
authors.initials: M
authors.lastname: Sumimoto
authors.forename: Daisuke
authors.initials: D
authors.lastname: Yokogawa
authors.forename: Masahiro
authors.initials: M
authors.lastname: Komeda
authors.forename: Hidetoshi
authors.initials: H
authors.lastname: Yamamoto
authors.forename: Kenji
authors.initials: K
authors.lastname: Hori
authors.forename: Hitoshi
authors.initials: H
authors.lastname: Fujimoto
mesh_terms: D000588:Amines / Q000737:chemistry*; D004159:Diphenylamine / Q000031:analogs & derivatives* / Q000737:chemistry*; D004583:Electrons; D008954:Models, Biological; D008958:Models, Molecular; D008962:Models, Theoretical; D008968:Molecular Conformation; D015394:Molecular Structure; D013056:Spectrophotometry, Ultraviolet; D013057:Spectrum Analysis; D013730:Terphenyl Compounds / Q000737:chemistry*
chemical_list: D000588:Amines; D013730:Terphenyl Compounds; D004159:Diphenylamine