Correlation effects on energy curves for proton transfer. The cation [H 5O 2] +

Abstract

Potential curves for proton transfer in [H 5O 2] + and for the dissociation of one OH bond in [H 3O] + were calculated by both ab initio and semi-empirical LCAO MO SCF CI methods. The energy barrier of the symmetric double minimum potential in [H 5O 2] + is very sensitive to electron correlation. At an OO distance of 2.74 Å it decreases from the HF value of 9.5 kcal/mole to about 7.0 kcal/mole. The results of the semi-empirical calculations agree well with the ab initio data as long as only relative effects are regarded. The partitioning of correlation energy into contributions of individual electron pairs is very similar for proton transfer in [H 5O 2] + and for the dissociation of one OH bond in [H 3O] +. In this example the proton transfer appears as a superposition of two “contracted ionic dissociation” processes. An interpretation of the behaviour of correlation during these processes is presented.