Double Proton Transfers in Dimers of Orthophosphoric, Sulfuric, and Perchloric Acids and in Therir Associates with Water Molecules

摘要

Mechanisms f proton transfer in the dimers of orthophosphoroc, sulfuric, and perchloric acids and in their associates with water molecules wwere stdied by MP2(fc)/6-31G~(**) ab initio calculations. It was shown that in akll these systems occurs cooperative(concerted or single-stage)transfer of two protons. The calculated activation barriers of cooperative proton transfer in the associates are equal to 9.1,8,7 and 10,3 kcal/mol, respectively, and in the dimers these values are -0.01,4.9, and 10.3 kcal/mol. The calculated results show that with increasing streength of H bonds in the system the barrier to double proton transfer decreases