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Implementation of Occupied and Virtual Edmiston–Ruedenberg Orbitals Using Cholesky Decomposed Integrals

Sarai Dery Folkestad, Regina Matveeva, Ida‐Marie Høyvik, Henrik Koch

2022Journal of Chemical Theory and Computation13 citationsDOIOpen Access PDF

Abstract

. The optimization is performed with all quantities in the molecular orbital basis, and the localization of the occupied orbitals is often less expensive than the corresponding self-consistent field (SCF) optimization. Furthermore, the occupied orbital localization scales linearly with the basis set. For the virtual space, the cost is significantly higher than the SCF optimization. The orbital spreads of the resulting virtual Edmiston-Ruedenberg orbitals are larger than for other, less expensive, orbital localization functions. This indicates that other localization procedures are more suitable for applications such as local post-Hartree-Fock calculations.

Topics & Concepts

Cholesky decompositionMolecular orbitalAtomic orbitalBasis setSlater-type orbitalComplete active spaceLocalized molecular orbitalsOrbital overlapPhysicsBasis functionBasis (linear algebra)ChemistryComputer scienceMolecular orbital theoryQuantum mechanicsElectronMathematicsDensity functional theoryGeometryMoleculeEigenvalues and eigenvectorsAdvanced Chemical Physics StudiesAdvanced NMR Techniques and ApplicationsMachine Learning in Materials Science
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