Greater transferability and accuracy of norm-conserving pseudopotentials using nonlinear core corrections

Area of Science:

• Computational Chemistry
• Materials Science
• Quantum Chemistry

Background:

• Pseudopotentials (PPs) with nonlinear core corrections (NLCC) are crucial for accurate electronic structure calculations.
• Assessing the transferability of these PPs across various functionals is essential for reliable predictions.

Purpose of the Study:

• To investigate the transferability of Goedecker, Teter, and Hutter (GTH) protocol PPs with NLCC across GGA, meta-GGA, and hybrid functionals.
• To evaluate the impact of these PPs on thermochemical and non-thermochemical properties.

Main Methods:

• Utilized GTH protocol pseudopotentials with nonlinear core corrections.
• Tested transferability across PBE, PBE0, ωB97X-V, and B97M-rV functionals.
• Compared results with all-electron calculations and reoptimized NLCC parameters.

Main Results:

• PBE-NLCC PP showed remarkable transferability to PBE0 and ωB97X-V functionals, significantly improving thermochemical benchmarks.
• Poor performance of B97M-rV with PBE-derived PP was mitigated by reoptimizing NLCC parameters.
• Atomization energies showed the greatest improvement, highlighting the importance of NLCC for covalent interactions.

Conclusions:

• GTH-NLCC PPs offer a reliable approach for various functionals, particularly for covalent interactions.
• NLCC provides a vital correction for atomization energies, enhancing accuracy in chemical reactivity studies.
• Combined with MOLOPT basis sets, NLCC-GTH PPs yield good results for condensed phase simulations.