Correlation-Consistent Gaussian Basis Sets for Solids Made Simple.

Area of Science:

• Quantum Chemistry
• Materials Science
• Computational Physics

Background:

• Simulating condensed-phase materials with quantum chemistry methods requires high-quality Gaussian basis sets for periodic calculations.
• Standard basis sets often exhibit linear dependencies in close-packed solids, causing numerical instability and hindering convergence to the complete basis set (CBS) limit, particularly in correlated calculations.

Purpose of the Study:

• To develop robust Gaussian basis sets optimized for periodic calculations.
• To address numerical stability issues encountered with standard basis sets in condensed-phase simulations.
• To ensure accurate and efficient convergence to the complete basis set (CBS) limit.

Main Methods:

• Revisiting Dunning's strategy for constructing correlation-consistent basis sets.
• Examining the trade-off between accuracy and numerical stability in periodic systems.
• Generating double-, triple-, and quadruple-zeta correlation-consistent Gaussian basis sets using Goedecker-Teter-Hutter (GTH) pseudopotentials.
• Limiting the number of primitive functions to avoid small exponents and ensure smooth CBS convergence.

Main Results:

• Developed new correlation-consistent Gaussian basis sets (double-, triple-, quadruple-ζ) for periodic calculations.
• Basis sets are suitable for main-group elements (first three rows) and exhibit reduced diffuseness for left-side elements compared to molecular sets.
• Demonstrated fast and reliable convergence to the CBS limit in Hartree-Fock and MP2 calculations.
• Verified performance using a test set of 19 semiconductors and insulators.

Conclusions:

• The newly developed Gaussian basis sets offer improved numerical stability for periodic quantum chemistry simulations.
• These basis sets facilitate accurate and efficient convergence to the complete basis set (CBS) limit for condensed-phase materials.
• The approach provides a reliable foundation for future simulations of solids and extended systems.