Polarized Gaussian basis sets from one-electron ions.

Abstract

We demonstrate that basis sets suitable for electronic structure calculations can be obtained from simple accuracy considerations for the hydrogenic one-electron ions Y(Y-1)+ for Y ∈ [1, Z], necessitating no self-consistent field calculations at all. It is shown that even-tempered basis sets with parameters from the commonly used universal Gaussian basis set (UGBS) [E. V. R. de Castro and F. E. Jorge, J. Chem. Phys. 108, 5225 (1998)] reproduce non-relativistic spin-restricted spherical Hartree-Fock total energies from fully numerical calculations to better accuracy than UGBS, which is shown to exhibit huge errors for some elements, e.g., 0.19 Eh for Th+ and 0.13 Eh for Lu, as it has been parameterized for a single atomic configuration. Having shown the feasibility of the one-electron approach, partially energy-optimized basis sets are formed for all atoms in the Periodic Table, 1 ≤ Z ≤ 118, by optimizing the even-tempered parameters for Z(Z-1)+. As the hydrogenic Gaussian basis sets suggested in this work are built strictly from first principles, polarization shells can also be obtained in the same fashion in contrast to previous approaches. The accuracy of the polarized basis sets is demonstrated by calculations on a small set of molecules by comparison to fully numerical reference values, which show that chemical accuracy can be reached even for challenging cases such as SF6. This approach is straightforward to extend to relativistic calculations and could facilitate studies beyond the established Periodic Table.