Norm-conserving Hartree–Fock pseudopotentials and their asymptotic behavior

2004/12/14 by J. R. Trail, R. J. Needs · 158 citations
Mathematics · Physics and Astronomy · #Boundary (topology) #Boundary value problem #Cold Atom Physics and Bose-Einstein Condensates #Core (optical fiber) #Inversion (geology) #Limit (mathematics) #Quantum Mechanics and Non-Hermitian Physics #Quantum nonlocality #Spectral Theory in Mathematical Physics #cond-mat.mtrl-sci

paper · pdf · doi:10.1063/1.1829049

published in The Journal of Chemical Physics 122(1), 14112 (American Institute of Physics) · 13 pages, 4 figures

openalex publication_date 2004/12/14 · arxiv created 2009/09/30 · arxiv updated 2009/12/01 · openalex created_date 2016/06/24 · openalex updated_date 2026/08/05

Abstract

We investigate the properties of norm-conserving pseudopotentials (effective core potentials) generated by inversion of the Hartree-Fock equations. In particular, we investigate the asymptotic behavior as r-->infinity and find that such pseudopotentials are nonlocal over all space, apart from a few special cases such as H and He. Such extreme nonlocality leads to a lack of transferability and, within periodic boundary conditions, an undefined total energy. The extreme nonlocality must therefore be removed, and we argue that the best way to accomplish this is a minor relaxation of the norm-conservation condition. This is implemented, and pseudopotentials for the atoms H-Ar are constructed and tested.

Citations

• Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals
• Electronic excitations: density-functional versus many-body Green’s-function approaches
• Soft self-consistent pseudopotentials in a generalized eigenvalue formalism

Cited by

• Smooth relativistic Hartree–Fock pseudopotentials for H to Ba and Lu to Hg
• Spectroscopic data for the LiH molecule from pseudopotential quantum Monte Carlo calculations