Bond critical points in the electronic structures of binary hydrides

Abstract

AbstractThe bond critical points of the binary hydrides formed by the elements of the first two rows of the periodic table have been calculated. Particular attention has been paid to the basis‐set dependence of the bond critical points at the experimental equilibrium geometries, or where necessary at model geometries. With the exception of H2S, stepwise extension of the basis set leads to a smooth convergence of the bond critical points to a set of values which appear to converge to the Hartree–Fock limit. For H2S it is shownb that the position of the bodn critical point is not only more sensitive to the presence of polarization functions in the basis set, but depends strongly on the orbital exponents of the polarization functions. Extensive optimizations of the exponents of the polarization functions have been carried out with the (12s9p/5s) basis set for second‐row hydrides. The effects of contracting the Huzinaga basis sets have been examined.