In this work, we present a robust implementation of the periodic Fock exchange for atom-centered Gaussian-type orbitals (GTOs). We discuss the divergence, appearing in the formulation of the periodic Fock exchange in the case of a finite number of k-points, and compare two schemes that remove it. These are the minimum image convention (MIC) and the truncated Coulomb interaction (TCI) that we use here in combination with k-meshes. We observe artifacts in four-center integrals of GTOs, when evaluated in the TCI scheme. They carry over to the exchange and density matrices of Hartree-Fock calculations for TCI but are absent in MIC. At semiconducting and insulating systems, we show that both MIC and TCI yield the same energies for a sufficiently large supercell or k-mesh, but the self-consistent field algorithm is more stable for MIC. We therefore conclude that the MIC is superior to TCI and validate our implementation by comparing not only to other GTO-based calculations but also by demonstrating excellent agreement with results of plane-wave codes for sufficiently large Gaussian basis sets.
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http://dx.doi.org/10.1021/acs.jctc.8b00122 | DOI Listing |
Ultramicroscopy
March 2025
Department of Materials, University of Oxford, 16 Parks Road, Oxford OX1 3PH, United Kingdom. Electronic address:
The rich information of electron energy-loss spectroscopy (EELS) comes from the complex inelastic scattering process whereby fast electrons transfer energy and momentum to atoms, exciting bound electrons from their ground states to higher unoccupied states. To quantify EELS, the common practice is to compare the cross-sections integrated within an energy window or fit the observed spectrum with theoretical differential cross-sections calculated from a generalized oscillator strength (GOS) database with experimental parameters. The previous Hartree-Fock-based and DFT-based GOS are calculated from Schrödinger's solution of atomic orbitals, which does not include the full relativistic effects.
View Article and Find Full Text PDFPhys Rev Lett
November 2024
Department of Physics and Astronomy, Johns Hopkins University, Baltimore, Maryland 21218, USA.
J Phys Chem A
November 2024
Department of Chemistry and Biochemistry, University of California, Santa Barbara, California, 93106, United States.
When trying to reach convergence of quantum chemical calculations toward the complete basis set limit, crystalline solids generally prove to be more challenging than molecules. This is due both to the closer packing of atoms─hence, to linear dependencies─and to the problematic behavior of Ewald techniques used for dealing with the infinite character of Coulomb sums. Thus, a dual basis set approach is even more desirable for periodic systems than for molecules.
View Article and Find Full Text PDFJ Chem Theory Comput
November 2024
Dipartimento di Chimica and NIS Centre, Università di Torino, Via P. Giuria 5, 10125 Torino, Italy.
J Phys Chem A
November 2024
Chair of Theoretical Chemistry, Department of Chemistry, Ludwig-Maximilians-Universität München, Butenandtstr. 5-13, Munich D-81377, Germany.
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