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

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 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 nonlocal. 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 frequencies of vibration of several dimers obtained with these HF pseudopotentials and plane waves are also in good agreement with all-electron results.