Efficient all-electron periodic Fourier-transformed Coulomb method.

Area of Science:

• Computational Chemistry
• Materials Science
• Solid-State Physics

Background:

• Accurate calculation of Coulomb matrices is crucial for electronic structure methods.
• Existing methods for periodic systems face computational challenges, especially with all-electron basis sets.
• Efficient algorithms are needed to handle large-scale solid-state density functional theory (DFT) calculations.

Purpose of the Study:

• To develop an efficient algorithm for constructing all-electron periodic Coulomb matrices.
• To enable faster and more accurate DFT calculations for solid-state systems.
• To improve the computation of cohesive and adsorption energies.

Main Methods:

• Combined Ewald summation with the Fourier-transformed Coulomb method.
• Utilized Gaussian density fitting for short-range interactions.
• Introduced an integral-direct plane wave density fitting scheme for long-range interactions.
• Applied dispersion-corrected PBE functional with all-electron basis sets.

Main Results:

• Achieved orders-of-magnitude speedups compared to range-separated density fitting.
• Successfully computed cohesive energy of benzene crystal and CO adsorption on MgO(001).
• Obtained results in good agreement with existing literature.

Conclusions:

• The new algorithm enables efficient Gaussian-based semi-local DFT calculations.
• Facilitates the use of dense k-point meshes and traditional molecular Gaussian basis sets.
• Paves the way for more extensive computational studies in solid-state chemistry and physics.