Ab initio study of hydrogen bonding in the H₃PO₂ dimer and H₃PO₂-DMF complex

The molecular structures and H-bonding interactions in the phosphinic acid dimer and the complex of phosphinic acid with N,N-dimethylformamide (DMF) were investigated by density functional theory calculations at the B3LYP level of theory. In order to better understand these phenomena, the individual molecules were also studied. The results were compared with previously obtained data for similar H-bonded complexes of phosphoric and phosphorous acids with DMF. Various correlations were found between geometric characteristics and parameters derived from Bader's theory and natural bond orbital analysis. Graphical abstract Irina V. Fedorova and Lyubov P. Safonova. Ab initio study of hydrogen bonding in the H₃PO₂ dimer and H₃PO₂-DMF complex. The acids of phosphorus are considered suitable candidates for ionomers due to their efficient proton transport properties. In order to better understand their molecular structures and their H-bond characteristics in real liquids, the most stable configurations of the H₃PO₂ dimer and the H₃PO₂-DMF complex were examined using computational methods in quantum chemistry. It was found that the strength of the H-bonding interactions in these systems depends strongly on the environment.