DFT study of the hydrogen bond strength and IR spectra of formic, oxalic, glyoxylic and pyruvic acids in vacuum, acetone and water solution

Abstract

The molecular geometries of the possible conformations of formic, oxalic, glyoxylic and pyruvic acids have been fully optimized at DFT B3LYP/6-311++G(d,p) levels of calculation in vacuum as well as in water and acetone solution. Solutions were treated according to the SCRF PCM approach but some formic acid–water and formic acid–acetone clusters as well as adducts of oxalic acid with two or four water molecules were also taken into account for testing the importance of specific solute–solvent effects. All the most stable isomers of the title compounds are characterized by weak intramolecular hydrogen bonds, whose strengths (EHB) cannot be correctly estimated as stability difference between the open and chelate forms since the energy of the former isomer is, in turn, stabilized by a weak hydrogen bridge due to the formic acid moiety. Following the Rotation Barrier Method (RBM), proposed some years ago, EHB in the examined molecules (gas phase) falls in the range of 18–22 kJ/mol for oxalic acid (9.6 kJ/mol for the c-C-t isomer), 16.8 kJ/mol for glyoxylic acid and 19.8 kJ/mol for pyruvic acid. Most of them disappear at all, or nearly at all, both in acetone and aqueous solution, in consequence of the solvent effect. The frequencies of the OH and CO stretching modes, calculated according to the anharmonic oscillator model, are in very good agreement with the experimental literature data, where available. Copyright © 2009 John Wiley & Sons, Ltd.