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Effects of external ions upon proton transfer reactions: H‐bonded systems containing HCOOH
Author(s) -
Scheiner Steve,
Das T.
Publication year - 1988
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560340713
Subject(s) - chemistry , ion , proton , polarization (electrochemistry) , ab initio , ab initio quantum chemistry methods , crystallography , computational chemistry , molecule , organic chemistry , physics , quantum mechanics
Ab initio calculations reveal that a cation, in a position equidistant from the two H‐bonding oxygen atoms of (HC(OH)O · H · OH 2 ) + , acts to push the proton from HCOOH toward OH 2 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 OH 2 by HCOOH suggests that polarization of the more distant subunit can also be a factor.