Theoretical study of gallium nitride molecules, GaN2 and GaN4

The electronic and geometric structures of gallium dinitride GaN 2, and gallium tetranitride molecules, GaN 4, were systematically studied by employing density functional theory and perturbation theory (MP2, MP4) in conjunction with the aug-cc-pVTZ basis set. In addition, for the ground-state of GaN 4( (2)B 1) a density functional theory study was carried out combining different functionals with different basis sets. A total of 7 minima have been identified for GaN 2, while 37 structures were identified for GaN 4 corresponding to minima, transition states, and saddle points. We report geometries and dissociation energies for all the above structures as well as potential energy profiles, potential energy surfaces and bonding mechanisms for some low-lying electronic states of GaN 4. The dissociation energy of the ground-state GaN 2 ( X (2)Pi) is 1.1 kcal/mol with respect to Ga( (2)P) + N 2( X (1)Sigma g (+)). The ground-state and the first two excited minima of GaN 4 are of (2)B 1( C 2 v ), (2)A 1( C 2 v , five member ring), and (4)Sigma g (-)( D infinityh ) symmetry, respectively. The dissociation energy ( D e) of the ground-state of GaN 4, X (2)B 1, with respect to Ga( (2)P) + 2 N 2( X (1)Sigma g (+)), is 2.4 kcal/mol, whereas the D e of (4)Sigma g (-) with respect to Ga( (4)P) + 2 N 2( X (1)Sigma g (+)) is 17.6 kcal/mol.