CNDO/2 Molecular orbital studies on π hydrogen bonding

Abstract

CNDO/2 molecular orbital calculations have been carried out on the hydrogen bonding of water and HF with the π-electrons of HCN, CH₃CN, C₂H₄, C₂H₂ and H₂CO. The dissociation energies of hydrogen bonds with the π-electrons of the triple bond are higher than those with the double bond in H₂CO. In the case of the interaction of water with HCN and CH₃CN, the hydrogen bond energies with the lone pairs and π-electrons are about the same. For the interaction of HF with a nitrile and an isonitrile, the dissociation energies are comparable.