Optimized norm-conserving Hartree-Fock pseudopotentials for plane-wave calculations

TL;DR

This paper introduces optimized Hartree-Fock pseudopotentials for plane-wave calculations that are finite at the origin, rapidly convergent, and improve computational efficiency while maintaining accuracy.

Contribution

It presents a new self-consistent method to develop norm-conserving HF pseudopotentials with improved convergence and physical properties for plane-wave electronic structure calculations.

Findings

Pseudopotentials show good agreement with all-electron HF atomic properties.

Dissociation energies and vibrational frequencies match all-electron results.

The method enhances plane-wave convergence for Hartree-Fock calculations.

Abstract

We report Hartree-Fock (HF) based pseudopotentials suitable for plane-wave calculations. Unlike typical effective core potentials, the present pseudopotentials are finite at the origin and exhibit rapid convergence in a plane-wave basis; the optimized pseudopotential method [A. M. Rappe et. al, Phys. Rev. B 41 1227--30 (1990)] improves plane-wave convergence. Norm-conserving HF pseudopotentials are found to develop long-range non-Coulombic behavior which does not decay faster than 1/r, and is non-local. This behavior, which stems from the nonlocality of the exchange potential, is remedied using a recently developed self-consistent procedure [J. R. Trail and R. J. Needs, J. Chem. Phys. 122, 014112 (2005)]. The resulting pseudopotentials slightly violate the norm conservation of the core charge. We calculated several atomic properties using these pseudopotentials, and the results are in good agreement with all-electron HF values. The dissociation energies, equilibrium bond lengths, and frequency of vibrations of several dimers obtained with these HF pseudopotentials and plane waves are also in good agreement with all-electron results.