Range-separated double-hybrid density-functional theory applied to periodic systems.

Area of Science:

• Computational chemistry
• Solid-state physics
• Quantum mechanics

Background:

• Accurate prediction of crystal binding energies is crucial for materials science.
• Traditional methods struggle with electron-electron interactions in periodic systems.
• Range-separated double hybrids combine density-functional approximations and Møller-Plesset perturbation theory.

Purpose of the Study:

• To implement and benchmark range-separated double hybrid methods for periodic systems.
• To evaluate the performance of these methods for various crystal types.
• To assess the suitability of standard range-separation parameters for solids.

Main Methods:

• Implementation of density-functional approximations for short-range and second-order Møller-Plesset (MP2) perturbation theory for long-range interactions.
• Application of the local correlation framework with Gaussian-type basis functions.
• Benchmarking on rare-gas, molecular, ionic, and covalent crystals.
• Testing spin-component-scaled MP2 for the long-range component.

Main Results:

• The range-separation parameter μ = 0.5 bohr(-1), commonly used for molecules, is effective for solids.
• Range-separated double hybrids achieve good accuracy for binding energies.
• Moderate basis sets like cc-pVDZ and aug-cc-pVDZ are sufficient.

Conclusions:

• Range-separated double hybrids are a promising approach for accurate solid-state calculations.
• The developed methods provide reliable binding energy predictions for diverse crystalline materials.
• This work validates the use of established parameters and basis sets in periodic systems.