A comparison of selected force constants derived from ab initioSCF calculations on β-hydroxyacrolein. Acrolein,performic acid,and formic acid

Harmonic force fields have been calculated for the planar hydrogen-bonded ring conformer of β-hydroxyacrolein, cCc, which is the most stable, and the chain conformer, cCt, generated by 180° rotation of O? H about the C? O bond axis. The equilibrium structure obtained using the 4-31 G basis set with full geometry optimization was employed in each case. Selected force constants for the bonds directly concerned in the formation of the ring from the chain structure, and the increments in going from the one to the other, are compared with the values for the corresponding conformers of performic and formic acids. As the ring size increases from four in trans-formic acid, to five in cis–cis-performic acid and to six in the cCc conformer of β-hydroxyacrolein there is a successive increase in the mechanical strength of the hydrogen-bridging unit. The energy changes for the chain → ring conversion do not follow this progression: performic acid is out of order. But, since a force constant is a localized bond property, whereas the energy changes are determined not only by interactions specific to the hydrogendonor and hydrogen-acceptor groups but also by interactions involving more distant parts of the molecule, the force constants for the bonds directly concerned in the formation of the hydrogen bridge provide a less ambiguous basis for comparing the strength of the intramolecular hydrogen bonding.