Four-proton migrations in associates of two molecules of formic acid with two molecules of water or hydrogen fluoride

Abstract

The mechanisms of proton transfer in associates of two molecules of formic acid with two molecules of water or hydrogen fluoride were studied usingab initio (SCF/6-31G**) method. Cooperative (concerted, or one-step) four-proton transfer occurs in the associates studied. The structures of the transition states are in complete agreement with the previously proposed concept of stereochemical correspondence for cooperative reactions. The calculated energy barriers to cooperative proton transfer in the associates investigated are 32.9 and 24.2 kcal mol−1, respectively.