The Vacuum Ultraviolet Absorption Spectra of Aniline and Some of Its N-Derivatives

Abstract

The vacuum ultraviolet absorption spectra of anilne, N-methylaniline, N-ethylaniline, N,N-dimethylaniline, N,N-diethylaniline and N-n-butylaniline have been measured in the vapor phase by a recording vacuum ultraviolet spectrophotometer, with which the absorption measurements have been extended down to 1500 Å. Some new bands have been found in the vacuum ultraviolet region, and in total five π→π* transtion bands with molar extinction coefficients larger than 1500 have been observed commonly for the anilines. In order to clarify the nature of these bands, a theoretical treatment has been made by considering the configuration interaction among the ground, locally excited and charge-transfer configrations. An excellent agreement has been obtained between the experimental and the calculated result. It has been concluded the the anilines studied here exhibit intramolecular charge-transfer bands characteristic if the electron trasfer interaction between the substituent and benzene ring.

Time‐dependent Hartree–Fock calculations in the Pariser–Parr–Pople model. Applications to aniline, azulene and pyridine

“…The experimental results are taken from Bibliography b Bibliography [ 1 71. [16]. The direction of the transition moment is determined for the two lowest excitations [17] by the film method [18].…”

“…The other moment directions are not determined experimentally. A review of calculation on the aniline singlet spectrum is given in Bibliography [16]. The results of the triplet excitation energies are given in Table 111.…”

Theoretical study of triplet-triplet absorption spectra of mono andp-di-substituted benzenes with electron-donating substituents

“…This kind of intramolecular interaction was first proposed by Nagakura and Tanaka [11] for the singlet-state transitions of substituted benzenes in order to explain the new K. Kinmra absorption bands rather than the bands pertinent to the benzene ring and the substituents. Nagakura and his co-workers, including the present author [12,13], have studied the near and vacuum ultra-violet absorption spectra and singlet electronic structures of various mono-substituted benzenes including phenols and anilines by using a theoretical method presented first by Longuet-Higgins and Murrell [14,15]; the observed spectra are interpreted well in terms of the intramolecular charge-transfer effect. In addition, the theoretical method used by Nagakura et al [12,13] has recently been extended to the calculation of the triplet energy levels for several substituted benzenes by Kimura and Tsubomura [16], who placed emphasis on the lowest triplet levels from which phosphorescence is emitted.…”

“…Nagakura and his co-workers, including the present author [12,13], have studied the near and vacuum ultra-violet absorption spectra and singlet electronic structures of various mono-substituted benzenes including phenols and anilines by using a theoretical method presented first by Longuet-Higgins and Murrell [14,15]; the observed spectra are interpreted well in terms of the intramolecular charge-transfer effect. In addition, the theoretical method used by Nagakura et al [12,13] has recently been extended to the calculation of the triplet energy levels for several substituted benzenes by Kimura and Tsubomura [16], who placed emphasis on the lowest triplet levels from which phosphorescence is emitted. It has been indicated that shifts of the phosphorescence spectra of the substituted benzenes from that of benzene may be interpreted in terms of the amount of the intramolecular CT contributions to the lowest triplet states.…”

Etude spectroscopique de l'aniline dans les solvants

“…Kimura et al (2), par une Ctude thtorique, laissent prtvoir que l'on est en prtsence "d'une bande de transfert, caracttristique d'un transfert de lYClectron entre les substituants et le cycle". 'Revision reCue le 10 janvier 1975.…”