A New Empirical Intermolecular Potential Energy Function for Hydrogen Bonding: Application to the Gas Phase and Solid State of Carboxylic Acids and Alcohols

Abstract

An empirical intermolecular potential energy function for carboxylic acids and alcohols has been derived for use in conformational energy calculations. The atom-atom interactions across the hydrogen bond include contributions from coulombic, dispersion, induction, polarization, repulsion, and a hydrogen bond shape function. The data used to refine the variable coefficients include electron diffraction structure of dimers of acetic and formic acids, intermolecular vibrational frequencies of dimers, gas-phase dipole moments, X-ray structures of crystalline carboxylic acids, thermodynamic dimerization and crystal lattice energy, and partial atomic charges from molecular orbital studies. Account is taken of charge migration upon formation of the hydrogen bond.KeywordsKcal MoleDonor HydrogenAcid DimerPartial Atomic ChargeCyclic DimerThese keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.