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Hydrogen Bonding and Proton Transfers Involving the Carboxylate Group
Journal of the American Chemical Society (1989)
  • Slawomir M. Cybulski
  • Steve Scheiner, Utah State University

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 C2, 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-0 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.

  • hydrogen bonding,
  • proton,
  • transfers,
  • caroxylate,
  • group
Publication Date
January 1, 1989
Publisher Statement
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
Citation Information
Hydrogen Bonding and Proton Transfers Involving the Carboxylate Group S. M. Cybulski and S. Scheiner J. Am. Chem. Soc., 1989 111 (1), 23-31.