Optimized Pseudopotentials and Basis Sets for Semiempirical Density Functional Theory for Electrocatalysis...

Area of Science:

• Computational Chemistry
• Materials Science
• Quantum Chemistry

Background:

• Accurate electronic structure calculations are crucial for understanding chemical and physical properties of materials.
• Existing pseudopotential and basis set combinations can introduce significant errors in density functional theory (DFT) calculations.
• Optimization of these computational tools is necessary for reliable predictions.

Purpose of the Study:

• To optimize Goedecker, Teter, and Hutter (GTH) norm-conserving pseudopotentials (PPs) and molecular optimized (MOLOPT) basis sets.
• To develop accurate computational methods for main-group elements, 3d, and noble metals using B97M-rV and ωB97X-V density functionals.
• To validate the performance of these optimized sets against experimental data and all-electron calculations.

Main Methods:

• Optimization of GTH norm-conserving pseudopotentials.
• Development of corresponding MOLOPT basis sets (DZVP, TZVP, TZV2P).
• Validation using all-electron calculations, ab initio molecular dynamics simulations, and comparison with experimental trends.

Main Results:

• The optimized PPs and MOLOPT basis sets show significant improvements over standard PBE defaults.
• Accurate prediction of redox reaction energies, geometries, and binding energies for metal monocarbonyls.
• Improved agreement with experimental trends for metal surface relaxations and CO adsorption on metal surfaces.

Conclusions:

• The developed GTH pseudopotentials and MOLOPT basis sets provide a more accurate and reliable approach for DFT calculations involving metals.
• These optimized sets enhance the predictive power of computational chemistry for materials properties and surface phenomena.
• The findings pave the way for more precise theoretical investigations in catalysis, surface science, and materials design.