Acta Chimica Slovaca (ACS) publishes papers on fundamental and applied aspects of chemistry, biochemistry, chemical technology, chemical engineering and process control, biotechnology and food technology. Welcome are also topics which include chemical aspects of materials, physical chemistry and chemical physics, analytical chemistry, macromolecular chemistry and biomedical engineering.

Torsional deformation effect on the N−H bond dissociation energy in diphenylamine

Peter Poliak *, Adam Vagánek

Institute of Physical Chemistry and Chemical Physics, Slovak University of Technology, Radlinského 9, SK-812 37 Bratislava, Slovakia

E-mail: *

Abstract: In this work, the influence of the inter-ring dihedral angles and their deformation on the energetics of diphenylamine molecule and its radical is investigated by the B3LYP/6-311++G** approach. Our approximated bond dissociation enthalpy of diphenylamine is 370.0 kJ mol–1 and it is in good agreement with the recently published experimental data. The potential functions of both the molecule and the radical with respect to the mutual aromatic ring orientations are presented. The potential function for the molecule is of a double-barrier type, whereas the radical possesses a single-barrier function. The calculated total electronic energies are used to approximate the change of the bond dissociation enthalpy with the twisting of the dihedral angle. The dependence of the bond dissociation enthalpy on the dihedral angle is represented by a single-barrier type function. The dependence of the nitrogen atom spin density on the studied dihedral angle is also discussed.

Keywords: DFT, industrial antioxidant, BDE, diphenylamine, torsional potential energy

Full paper in Portable Document Format: acs_0164.pdf

Acta Chimica Slovaca, Vol. 6, No. 2, 2013, pp. 182—186, DOI: 10.2478/acs-2013-0029