Hydrogen Bonding and Proton Transfers Involving the Carboxylate Group

Document Type


Journal/Book Title

Journal of the American Chemical Society

Publication Date



American Chemical Society




The complex formed between HCOO- and HOH is examined by ab initio methods using a 4-31+G* basis set. A number of minima are located in the potential energy surface, the most stable of which is of C2v geometry wherein both protons of HOH participate in H bonds. The barrier impeding proton transfer between OH- and HCOO- rises with increasing intermolecular separation for each of the arrangements studied. As the OH- anion moves toward the C-O axis of HCOO-, the equilibrium position of the bridging proton is shifted toward the former group, paralleling earlier observations for the pair of neutral subunits HCOOH and HOH. On the other hand, HCOO- and HCOOH behave in different fashion with respect to motions of the hydroxyl group out of the carboxyl plane. These patterns are explained simply on the basis of differing ion-dipole interactions, as are small differences in the optimal geometries and proton-transfer behavior of the various arrangements of the two subunits.


Originally published in the Journal of the American Chemical Society by the American Chemical Society . Publisher’s PDF available through remote link. DOI: 10.1021/ja00183a004

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