title: Effect of Lone Pairs on Molecular Resonance Energy.
abstract: In an effort to understand the theoretical parameters of charge-shift bonding, computational experiments have been designed to elucidate the factors effecting molecular resonance energy. Valence bond theory calculations have been used to calculate resonance energies of homonuclear bonds in the series [HnX-XHn]Z, where n = 0-3 and Z = 2n - 6, 2n - 4, 2n - 2, and 2n for X = C, N, O, and F, respectively. It is shown that the resonance energy decreases as the number of lone pairs increases. Calculated orbital contraction coefficients show that this unexpected result is due to the dominance of orbital size over the lone-pair effect. These results are irrespective of the HXX bond angles. It is also shown that the resonance energy increases with decreasing HXX bond angles due to the increase in p character in the bonding orbital.
authors.affiliation: Department of Chemistry, Biochemistry, and Physics, Marist College , 3399 North Road, Poughkeepsie, New York 12601, United States.
authors.forename: Croix J
authors.initials: CJ
authors.lastname: Laconsay
authors.affiliation: Department of Chemistry, Biochemistry, and Physics, Marist College , 3399 North Road, Poughkeepsie, New York 12601, United States.
authors.forename: Andrew M
authors.initials: AM
authors.lastname: James
authors.affiliation: Department of Chemistry, Biochemistry, and Physics, Marist College , 3399 North Road, Poughkeepsie, New York 12601, United States.
authors.forename: John Morrison
authors.initials: JM
authors.lastname: Galbraith