AB-INITIO MO STUDY OF DIPHENYLAMINE DERIVATIVES - DIPHENYLAMINE, DIPHENYLAMINIUM, DIPHENYLAMINYL AND DIPHENYLNITROXIDE

The electronic structures of four diphenylamine derivatives: diphenylamine, diphenylaminium, diphenylaminyl and diphenylnitroxide, often used in ferromagnetic model-polymers as a spin accommodator, are described using ab initio molecular orbital methods in the RHF, UHF and ROHF schemes at the STO-3G and 6-31G levels of calculation. The four 'skewed', 'planar, 'book' and 'morino' conformations related to the torsional motion characteristic of diphenyl molecules are examined in detail on the basis of the present calculations. The skewed conformation is predicted to be the most favourable of these molecules. The calculated geometrical parameters are in good agreement with the experimental results already reported.