Complete and Orthonormal Sets of Exponential-type Orbitals with non-integer quantum numbers. On the results for many-electron atoms using Roothaan's LCAO method

Abstract: Complete orthonormal sets of exponential-type orbitals with non-integer principal quantum numbers are discussed as basis functions in non-relativistic Hartree-Fock-Roothaan electronic structure calculations of atoms. A method is proposed to construct accurate and computationally efficient basis sets using these orbitals. It is demonstrated that principal quantum numbers of fractional order cannot be treated solely as variational parameters, since such a procedure may lead to unphysical basis sets (in particular, linearly dependent Slater-type functions). Ground-state total energies for the Be- and Ne- isoelectronic series are calculated. The results obtained are lower than those reported using other published basis sets. However, the energies obtained using Slater-type functions with non-integer principal quantum numbers are omitted from the comparison. These "orbitals" have no physical interpretation (except the "1s", which coincides with a hydrogenlike eigenfunction). In general linear independence of such Slater-type orbitals is not guaranteed. The results confirm that the parameter alpha, used to represent the complete orthonormal exponential-type orbitals in the weighted Hilbert space, is neither observable nor suitable to be considered as a variational parameter, despite its treatment as such in some prior work.