Desymmetrization in geometry optimization: application to an ab initio study of copper(I) hydration

Group theoretical arguments are used to find the subgroup corresponding to symmetry reduction along a particular irreducible representation of a group. The results are used to guide the search for stationary points on the potential energy surface of hydrated copper(I) ion at the HF/6-31G*, HF/6-31+G*, HF/6-311+G*, MP2/6-31G*, MP2/6-31+G*, MP2/6-311+G*, B3LYP/6-31G*, B3LYP/6-31+G*, and B3LYP/6-311+G* levels. The better levels give the most stable coordination number of two. The effect of desymmetrization on the Cu-O distances and stretching frequencies has been examined.