Journal of Physical Chemistry A, Vol.119, No.24, 6528-6541, 2015
Bonding Motifs of Noble-Gas Compounds As Described by the Local Electron Energy Density
The bonding situation of some exemplary noble-gas (Ng) compounds, including HNg(+), HNgF, FNgO(-), Ng-HF, and Ng BeO (Ng = He-Xe) was assayed by examining their local electron energy density H(r). In general, this function partitions the space of atomic species (neutral and ionic) into inner regions of negative values and outer regions of positive values. In the formation of chemical bonds, these atomic regions combine so to form a molecular H(r), H-mol(r), whose plotted form naturally shows the "covalent" and "noncovalent" regions of the molecular species and allows also the recognition of different types of noncovalent interactions such van der Wags, hydrogen, and ionic or partially ionic bonds. The qualitative assignment of the various bonding motifs is corroborated by the topological analysis of H-mol(r), which typically includes several critical points of rank 3 and variable signature. These points are, in particular, characterized here in terms of their bond degree (BD). From a previous definition (Espinosa et al. J. Chem. Phys. 2002, 117, 5529-5542), this quantity is taken as the ratio between the energy density calculated at the critical point of H(r), H(r(c)), and the corresponding electron density rho(r(c)): BD = -H(r(c))/rho(r(c)). Thus, the BD is positive for covalent interactions (H(r(c)) < 0) and negative for noncovalent interactions (H(r(c)) > 0). For structurally related species, the BD result, in general, positively correlated with the binding energies and is, therefore, a semiquantitative index of stability. The present study suggests the general validity of the H-mol(r) to effectively assay the bonding motifs of noble-gas compounds.