Infrared Intensification and Hydrogen Bond Stabilization: Beyond Point Charges.

Abstract

Infrared band intensification of the A-H bond stretching mode of A-H···B acid-base systems has long been known to be the most spectacular spectral change occurring on hydrogen bonding. A QTAIM/CCTDP model is reported here to quantitatively explain the electronic structure origins of intensification and investigate the correlation between experimental enthalpies of formation and infrared hydrogen bond stretching intensifications amply reported in the literature. Augmented correlation-consistent polarized triple-zeta quantum calculations at the MP2 level were performed on complexes with HF and HCl electron acceptors and HF, HCl, NH3, H2O, HCN, acetonitrile, formic acid, acetaldehyde, and formaldehyde electron donor molecules. The A-H stretching band intensities are calculated to be 3 to 40 times larger than their monomer values. Although the acidic hydrogen atomic charge is important for determining the intensities of HF complexes relative to HCl complexes with the same electron donor, they are not important for infrared intensifications occurring on hydrogen bond formation for a series of bases with a common acid. Charge transfers are found to be the most important factor resulting in the intensifications, but dipolar polarization effects are also significant for each series of complexes. A mechanism involving intra-acid and intermolecular electron transfers as well as atomic polarizations is proposed for understanding the intensifications. The calculated sums of the intermolecular electron transfer and acid dipolar polarization contributions to the dipole moment derivatives for each series of complexes are highly correlated with their enthalpies of formation and H-bond intensifications. This could be related to increasing electron transfer from base to acid that correlates with the calculated hydrogen bonding energies and may be a consequence of the A-H bond elongation on complex formation having amplitudes similar to those expected for the A-H vibration.