A study of the bonded interactions in nitride molecules in terms of bond critical point properties and relative electronegativities

Bond critical point properties calculated for the MN bonds in a number of geometry optimized nitride molecules containing first- and second-row M cations are compared with those calculated for a number of oxide molecules. As reported for the oxides, the value of the electron density, ρ(r _c ), at the bond critical points, r _c , increases with decreasing bond length while for the more electronegative cations, the local energy density, H(r _c ) decreases nonlinearly in value as the relative electronegativities of the M-cations, χ _M , tend to increase. In the majority of cases, χ_M, |λ₁|/λ₃ and ∇²ρ(r _c ) increase with decreasing minimum energy bond lengths. The bond lengths adopted by the molecules are indicated to be an important determinant of the critical point properties of the electron density distributions. The relative electronegativities derived from the electron density distributions of the nitrides agree with those derived for the oxides and Pauling’s electronegativities to within ∼5%, on average. Received: 3 February 1997 / Revised, accepted: 11 July 1997