Substituent Effects on the Quantum Interference of Two-Center One-Electron Bonds: [BX] (X = H, F, Cl, CN, OH, CH, and OCH).

The interference energy analysis (IEA) provided by the generalized product function energy partitioning (GPF-EP) method was applied to investigate the influence of the neighboring atoms on the nature of the two-center one-electron (2c1e) bonds in the anion dimers of BX species (X = H, F, Cl, CN, OH, CH, and OCH). The species were studied at the GVB-PP(6/12).SC(1,2)/6-31**G++ level of calculation. The IEA has revealed that there is a balance between two main factors determining the chemical stability of the species. Quantum interference acts as the sole stabilizing effect in the formation of the chemical bonds, particularly as the result of the drop in kinetic energy, and the electronegativity of the substituent has a direct influence on the magnitude of this effect. The quasi-classical energy is responsible for the destabilizing factors, mainly the group bulkiness, and the "electron-withdrawing" effect in the case of the cyano group.