Valence Bond Study of the Hydrogen Bond. III. Formation and Migration of Ionic Defects in Water and Ice

Abstract

Potential energy curves of the proton for the formation and migration of the ionic defects in water and ice are calculated by a valence bond method. In order to explain the thermodynamical data on the dissociation of water and ice, the reaction field concept of Onsager is introduced. The potential energy for the migration of positive and negative defects is calculated with six valence bond structures. The resulting height of the potential barrier for the positive defect is lower than that for the negative one, and this agrees with the experimental fact that the mobility of the positive defect is much greater than the negative one. The experimental data on the mobility of the positive defect in ice can be explained by Gosar's theory if the O–O distance is taken to be 2.63 Å