Hydrogen Bonding and Proton Transfers Involving the Carboxylate Group

Authors

Slawomir M. Cybulski
Steve Scheiner, Utah State UniversityFollow

Document Type

Article

Journal/Book Title

Journal of the American Chemical Society

Publication Date

1-1989

Publisher

American Chemical Society

Volume

111

Abstract

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 C_2v 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.

Comments

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

Recommended Citation

Hydrogen Bonding and Proton Transfers Involving the Carboxylate Group S. M. Cybulski and S. Scheiner J. Am. Chem. Soc., 1989 111 (1), 23-31.