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arXiv · 1811.05777

Quantum chemistry with Coulomb Sturmians: Construction and convergence of Coulomb Sturmian basis sets at Hartree-Fock level

Michael F. Herbst·James Emil Avery·Andreas Dreuw
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Abstract

The first discussion of basis sets consisting of exponentially decaying Coulomb Sturmian functions for modelling electronic structures is presented. The proposed basis set construction selects Coulomb Sturmian functions using separate upper limits to their principle, angular momentum and magnetic quantum numbers. Their common Coulomb Sturmian exponent is taken as a fourth parameter. The convergence properties of such basis sets are investigated for second and third row atoms at the Hartree-Fock level. Thereby important relations between the values of the basis set parameters and the physical properties of the electronic structure are recognised. For example, an unusually large limit for the angular momentum quantum number in unrestricted Hartree-Fock calculations can be linked to the breaking of spherical symmetry in such cases. Furthermore, a connection between the optimal, i.e. minimum-energy, Coulomb Sturmian exponent and the average Slater exponents values obtained by Clementi and Raimondi (E. Clementi and D. L. Raimondi, J. Chem. Phys. 38, 2686 (1963)) is made. These features of Coulomb Sturmian basis sets emphasise their ability to correctly reproduce the physical features of Hartree-Fock wave functions.

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Michael F. Herbst, James Emil Avery, Andreas Dreuw. 2019-01-04. Quantum chemistry with Coulomb Sturmians: Construction and convergence of Coulomb Sturmian basis sets at Hartree-Fock level. https://doi.org/10.1103/physreva.99.012512

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