Spin in density‐functional theory
By Christoph R. Jacob, Markus Reiher. 2012
241 citations recorded by the source corpus.
The accurate description of open-shell molecules, in particular of transition metal complexes and clusters, is still an important challenge for quantum chemistry. Although density-functional theory (DFT) is widely applied in this area, the sometimes severe limitations of its currently available approximate realizations often preclude its application as a predictive theory. Here, we review the foundations of DFT applied to open-shell systems, both within the nonrelativistic and the relativistic framework. In particular, we provide an in-depth discussion of the exact theory, with a focus on the role of the spin density and possibilities for targeting specific spin states. It turns out that different options exist for setting up Kohn–Sham DFT schemes for open-shell systems, which imply different definitions of the exchange–correlation energy functional and lead to different exact conditions on this functional. Finally, we suggest possible directions for future developments. © 2012 Wiley Periodicals, Inc.
Subfields: Atomic and Molecular Physics, and Optics, Electronic, Optical and Magnetic Materials, Organic Chemistry
View Paper: https://www.semanticscholar.org/paper/290682493b644be1cd9a45a0f55623fca880a33c
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In Atomic and Molecular Physics, and Optics
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- Krysta Marie Svore
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In Electronic, Optical and Magnetic Materials
In Organic Chemistry
Citations in the corpus
- Elucidating reaction mechanisms on quantum computers (2016, background): “In these unrestricted DFT calculations, the spin symmetry was broken [73] and only Sz remains as a good quantum number.”
- Status and Challenges of Density Functional Theory (2020, background): “For example, even in the absence of spin-orbit coupling, the variationally best Slater determinant for an open-shell system will be spin polarized (sometimes called spin unrestricted or just unrestricted), which means that the spin-up orbitals are not the same as the spin-down ones, and the Slater d”
- Density functional theory: Foundations reviewed (2014, methodology): “Moreover, the errors generated by the commonly used functionals do not show systematic trends in the prediction of molecular properties [122–130].”