Variation with the intermolecular distance of properties dependent on the electron density in cyclic dimers with two hydrogen bonds

The variation with the intermolecular distance of geometries, energies, and other properties dependent on the electron density rho(r) are studied in three cyclic dimers linked by two hydrogen bonds: formic acid and formamide homodimers and the heterodimer formamide/formic acid complex. Topological features, energy densities and integrated atomic properties provided by AIM theory are calculated with rho(r) obtained at B3LYP/6-311++G(d,p) optimized geometries for a number of intermonomer distances covering large separations, equilibrium, and short distances. The variation with these distances of properties studied allows to characterize the nature of the interaction in A-H.B (A=N, O and B=O) hydrogen bonds. Whereas at large distances the attraction is purely electrostatic, quantum effects associated with redistributions of rho(r) mainly around H and B atoms dominate the interaction in the neighborhood of equilibrium. Mutual penetration of the electron densities of these atoms leads to considerable reductions of their atomic volumes and associated polarization effects as well as energetic stabilization of atom A. Although the interaction in this range of intermonomer separations displays noncovalent features, when the dimers move at distances shorter than equilibrium, characteristics typical of covalent interactions begin to appear while the systems leave the planar structures presented until then. This work complements our previous study [O. Galvez, P. C. Gomez, and L. F. Pacios, J. Chem. Phys. 115, 11166 (2001)] of dimers with one single hydrogen bond. (C) 2003 American Institute of Physics.