Ab initio inter-radical potential for p-phenylenediamine radical cation dimer

Abstract

Ab initio molecular orbital calculations were carried out to investigate the inter-radical interaction of the paired p-phenylenediamine radical cations in the singlet state. After initial optimization of the dimer in the parallel sandwich ( D 2 h ) and parallel displaced ( C s ) configurations at the B3LYP/6-31G* theoretical level, the MP2/6-31G* and B3LYP/6-31G* single energies of the dimer were calculated as a function of the inter-radical distance R. The depths of the potential minima near R=3.2 Å were estimated to be in the order of the hydrogen bonding energy, assuming that the electrostatic contribution between the cations is canceled out by the attractive contributions due to the counter anions on the aspect of a simple electrostatic model. This can be related to the indications of the cation dimer formation in solution in the presence of counter anions at a low temperature reported previously in the literature by resonance Raman and electronic absorption spectra. The inter-radical (Raman active) frequencies of the dimer were calculated, one of which corresponds to the reported value at 161 cm −1 observed in the resonance Raman spectrum in ethanol at 200 K by Yokoyama and Maeda (Chem. Phys. Lett. 48 (1977) 59).