Chemical Reactivity Within the Spin‐Polarized Framework of Density Functional Theory

Chamorro, Eduardo; Pérez, Patricia

doi:10.1002/9781119683353.ch8

Cited by 1 publication

(1 citation statement)

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“…The kinetic energy is known to be the most challenging energy to be expressed explicitly as a density-functional. For this reason, Kohn-Sham (KS) DFT [1] is the most common theory within DFT that is utilized for practical calculations and to derive concepts, [2,3] as KS-DFT uses single-electron orbitals to determine a kinetic energy. As is well known, even though KS-DFT practical calculations perform well for determining properties such as molecular geometries, and optoelectronic properties of a very large number of compound types, it is difficult for transitionmetal systems, [4] bond-breaking, [5] and charge-transfer excitations, [6] among others, where erroneous charge delocalization [7][8][9][10] is a main manifestation of these adverse effects.…”

Section: Introductionmentioning

confidence: 99%

Cluster Amplitudes and Their Interplay with Self‐Consistency in Density Functional Methods

2022

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Density functional theory (DFT) provides convenient electronic structure methods for the study of molecular systems and materials. Regular Kohn‐Sham DFT calculations rely on unitary transformations to determine the ground‐state electronic density, ground state energy, and related properties. However, for dissociation of molecular systems into open‐shell fragments, due to the self‐interaction error present in a large number of density functional approximations, the self‐consistent procedure based on the this type of transformation gives rise to the well‐known charge delocalization problem. To avoid this issue, we showed previously that the cluster operator of coupled‐cluster theory can be utilized within the context of DFT to solve in an alternative and approximate fashion the ground‐state self‐consistent problem. This work further examines the application of the singles cluster operator to molecular ground state calculations. Two approximations are derived and explored: i) A linearized scheme of the quadratic equation used to determine the cluster amplitudes. ii) The effect of carrying the calculations in a non‐self‐consistent field fashion. These approaches are found to be capable of improving the energy and density of the system and are quite stable in either case. The theoretical framework discussed in this work could be used to describe, with an added flexibility, quantum systems that display challenging features and require expanded theoretical methods.

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