Proton transfers in hydrogen-bonded systems V. Analysis of electronic redistributions in (N2H7)+

Abstract

The transfer of the central proton between the two NH3 units of (H3NHNH3)+ is studied using the 4–31 G basis set within the ab-initio Hartree-Fock formalism. Electron density difference maps are constructed which clearly indicate electronic redistributions which accompany the half-transfer of the proton from its equilibrium position (NHN) to the midpoint of the hydrogen bond (NHN). The overall loss of electronic charge from the proton-accepting molecule originates in three distinct regions of space, while a density buildup of smaller magnitude is observed in a characteristic region centered about the N nucleus. Similar regions are noted for the proton-donating molecule, although the changes are reversed in sign. A partitioning of the total density changes into contributions from the various molecular orbitals demonstrates that the a1 orbitals are associated with density shifts along the H-bond axis. Changes in the N lone pairs are attributed chiefly to the (5a1,6a1) pair and are somewhat attenuated by opposite shifts involving the (3a1. 4a1) pair. Orbitals of e symmetry lead to polarizations of the NH bonds and density shifts perpendicular to the H-bond axis.