Simple one-centre calculation of breathing force constants and equilibrium internuclear distances for NH3, H2O and HF

Abstract

Total molecular energies, breathing force constants and equilibrium internuclear distances are determined for the NH₃, H₂O and HF molecules using a single determinant wave function of the simplified one-centre form s ² s′² p _x ² p _y ² p _z ², where each of the five Slater orbitals, s, s′, p _x , p _y , p _z , is characterized by an effective orbital exponent ζ and an effective principal quantum number n. Five different calculations are performed for each molecule: in (a) the orbitals are centred on the heavy atom, the parameters n are taken to be integral, and the orbitals p _x , p _y and p _z are given the same ζ values (the spherical approximation); in (b) the orbitals p _x , p _y and p _z are allowed to have different ζ values (the ellipsoidal approximation); (c) and (d) are the same as (a) and (b) except that non-integral n values are allowed; (e) is the same as (d) except that the orbital centre also is taken to be a variational parameter. The values obtained are compared with experimental values (the agreement is surprisingly good) and with values from previous one-centre wave functions. The electronic densities for the various spherical approximations are tabulated.