language: en

Analysis of the Electronic Factors Controlling the N„ and the First two «(***, bt) Photoelectron Ionizations in N-Containing Monosubstituted Benzenes (Ph—NRR' and Ph—N=X)

Francesco Paolo Colonna, Giuseppe Distefano, and Derek Jones,
Istituto dei Composti del Carbonio Contenenti Eteroatomi e Loro Applicazioni del C. N. R.,
Ozzano-Emilia (Bologna), Italy
Alberto Modelli
Istituto Chimico "G. Ciamician" deirUniveraita di Bologna,
Via Selmi 2 , Bologna , Italy
and Vinicio Galasso
Dipartimento di Chimica dell'Universita,
Trieste , Italy
Z. Naturforsch. 86a», 385—390 (1081);

[received February 16 1981]

The first two 71(02, b\ ) IE*B of monosubstituted benzenes containing di- and tri-coordinated nitrogen directly linked to the ring have been measured and analysed together with the Nu IE. These photoelectron properties are found to respond in the same sense, though to different ex* tents, to inductive and mesomeric interactions that the N-containing substituents sustain with the aromatic ring. The different sensitivities of these properties to substituent changes are discussed in connection with mechanisms of transmission of electronic effects with the aid of the ground state electronic structures determined by means of ab-initio calculations. The relative contribution of the relaxation energy to the considered core and valence IE'» is also examined by referring to the model used by Gelius and Siegbahn. The factors determining the apparently anomalous behaviour of nitrobenzene are discussed.

Introduction