Effects of External Ions upon Proton Transfer Reactions. H-Bonded Systems Containing HCOOH
Document Type
Article
Journal/Book Title
International Journal of Quantum Chemistry
Publication Date
3-1988
Publisher
Wiley-Blackwell
Volume
34
Issue
15
First Page
137
Last Page
147
Abstract
Ab initio calculations reveal that a cation, in a position equidistant from the two H-bonding oxygen atoms of (HC(OH)O · H · OH2)+, acts to push the proton from HCOOH toward OH2 if the ion is located near the —OH or CH group of HCOOH. In contrast, rotation of the cation out of the HCOOH plane, while maintaining its position relative to the two H-bonding atoms, leads to a potential which is little different than that observed in the absence of an ion. These findings are readily explained on the basis of ion-induced internal polarization of the subunit to which the ion is closer. Replacement of OH2 by HCOOH suggests that polarization of the more distant subunit can also be a factor.
Recommended Citation
Effects of External Ions upon Proton Transfer Reactions. H-Bonded Systems Containing HCOOH S. Scheiner and T. Das Int. J. Quantum Chem., 1988 34, Issue S15, 137-147.
Comments
http://onlinelibrary.wiley.com/doi/10.1002/qua.560340713/abstract
Publisher PDF is available for download through the link above.
Published by Wiley-Blackwell in International Journal of Quantum Chemistry