Hydrogen bonding: a molecular orbital treatment by the EHT and the CNDO/2 methods of methanol and of formic acid

Abstract

By both the EHT and the CNDO/2 calculations, the linear dimer of methanol is found to be more stable than the cyclic dimer. The hydrogen bonds in the trimer are stronger than those in linear dimers. The proton potential function, charge densities, and overlap populations in the linear dimer of methanol have been obtained. The CNDO/2 calculations show that the cis-form of formic acid is more stable than the trans-form, in agreement with experimental data. The cyclic dimer of formic acid is more stable than the open dimer. The β-form of formic acid trimer is more stable than the α-form. The proton potential function and the charge densities in the cyclic dimer of formic acid have been obtained. The CNDO/2 method gives more realistic proton potential functions for the dimers of methanol and formic acid. The O···O stretching force constant in the dimers of methanol and formic acid have been estimated to be 0.13×10⁵ dynes/cm and 0.27×10⁵ dynes/cm, respectively, in agreement with experimental data.