Affiliations: University of Guanajuato, Facultad de Química, Noria Alta s/n. Guanajuato, Gto., 36050, México | [x] Department of Chemistry, University of Patras, Greece | [y] Departamento de Quimica, CINVESTAV, Centro De Investigacion Y De Estudios Avanzados, Av. Instituto Politecnico Nacional, 2508, A.P. 14-740, Mexico, D.F. 07000, Mexico
Abstract: In this paper we study the small NaN+ (N ⩽ 12) cationic clusters fragmentation channels, with all electronic calculations performed at the B3LYP/6–311G+(d,p) DFT level of theory. For these cluster sizes, we obtain for all neutral, cationic, bi-cationic and anionic species the optimized geometries, total energies and electronic properties such as the adiabatic ionization potentials, electron affinities and global hardnesses. Furthermore, we propose the novel concept of global hardness change, Δη, within the conceptual DFT formalism, based on the maximum hardness principle of Chattaraj, Lee, and Parr. Thereafter we compute for all possible fragmentation channels the involved energetics, ΔE, and the global hardness change, Δη, both methods are shown to be in agreement with available experimental findings for all but one case. We show that hardness and the global hardness change are good DFT descriptors to assess the preferred fragmentation channels, where formation of the hardest fragments seems to be the driving force.
