Ab initiostudy of bonding trends among the 14-electron diatomic systems: from B24-to F24+

Hartree-Fock 6-31G* calculations give local minima for thirty-two 14-electron diatomic species, ranging in charge from B2 4- to F2 4+ or HeS4+. Of them, the calculations for the 13 species B2 4-, BC3-, BeC4-, BeN3-, BeO2-, BeNa+, BeMg2+, FO3+, F2 4+, HeP3+, HeS4+, LiMg+ and NNe3+ are new. The bond lengths of the negative species are compared with those in solids. Rough estimates are made for the heats of formation of the unknown salts fo BN2- and BO-. Møller-Plesset calculations are reported for the new posititive species and for the carbide. The calculated value of D 0 0 (LiMg+) 0·78 eV, is much larger than the experimental value of 0·09(9)eV.