## Perspective: Kohn-Sham density functional theory descending a staircase

## Abstract

This article presents a perspective on Kohn-Sham density functional theory (KS-DFT) for electronic structure calculations in chemical physics. This theory is in widespread use for applications to both molecules and solids. We pay special attention to several aspects where there are both concerns and progress toward solutions. These include: The treatment of open-shell and inherently multiconfigurational systems (the latter are often called multireference systems and are variously classified as having strong correlation, near-degeneracy correlation, or high static correlation; KS-DFT must treat these systems with broken-symmetry determinants). The treatment of noncovalent interactions. The choice between developing new functionals by parametrization, by theoretical constraints, or by a combination. The ingredients of the exchange-correlation functionals used by KS-DFT, including spin densities, the magnitudes of their gradients, spin-specific kinetic energy densities, nonlocal exchange (Hartree-Fock exchange), nonlocal correlation, and subshell-dependent corrections (DFT+U). The quest for a universal functional, where we summarize some of the success of the latest Minnesota functionals, namely MN15-L and MN15, which were obtained by optimization against diverse databases. Time-dependent density functional theory, which is an extension of DFT to treat time-dependent problems and excited states. Furthermore, the review is a snapshot of a rapidly moving field, and—like Marcel Duchamp—we hope tomore »

- Authors:

- Univ. of Minnesota, Minneapolis, MN (United States)

- Publication Date:

- Research Org.:
- Univ. of Minnesota, Minneapolis, MN (United States). Department of Chemistry, Chemical Theory Center, and Supercomputing Institute

- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

- OSTI Identifier:
- 1464926

- Alternate Identifier(s):
- OSTI ID: 1328549

- Grant/Contract Number:
- SC0012702; SC0015997

- Resource Type:
- Accepted Manuscript

- Journal Name:
- Journal of Chemical Physics

- Additional Journal Information:
- Journal Volume: 145; Journal Issue: 13; Journal ID: ISSN 0021-9606

- Publisher:
- American Institute of Physics (AIP)

- Country of Publication:
- United States

- Language:
- English

- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

### Citation Formats

```
Yu, Haoyu S., Li, Shaohong L., and Truhlar, Donald G. Perspective: Kohn-Sham density functional theory descending a staircase. United States: N. p., 2016.
Web. doi:10.1063/1.4963168.
```

```
Yu, Haoyu S., Li, Shaohong L., & Truhlar, Donald G. Perspective: Kohn-Sham density functional theory descending a staircase. United States. doi:10.1063/1.4963168.
```

```
Yu, Haoyu S., Li, Shaohong L., and Truhlar, Donald G. Wed .
"Perspective: Kohn-Sham density functional theory descending a staircase". United States. doi:10.1063/1.4963168. https://www.osti.gov/servlets/purl/1464926.
```

```
@article{osti_1464926,
```

title = {Perspective: Kohn-Sham density functional theory descending a staircase},

author = {Yu, Haoyu S. and Li, Shaohong L. and Truhlar, Donald G.},

abstractNote = {This article presents a perspective on Kohn-Sham density functional theory (KS-DFT) for electronic structure calculations in chemical physics. This theory is in widespread use for applications to both molecules and solids. We pay special attention to several aspects where there are both concerns and progress toward solutions. These include: The treatment of open-shell and inherently multiconfigurational systems (the latter are often called multireference systems and are variously classified as having strong correlation, near-degeneracy correlation, or high static correlation; KS-DFT must treat these systems with broken-symmetry determinants). The treatment of noncovalent interactions. The choice between developing new functionals by parametrization, by theoretical constraints, or by a combination. The ingredients of the exchange-correlation functionals used by KS-DFT, including spin densities, the magnitudes of their gradients, spin-specific kinetic energy densities, nonlocal exchange (Hartree-Fock exchange), nonlocal correlation, and subshell-dependent corrections (DFT+U). The quest for a universal functional, where we summarize some of the success of the latest Minnesota functionals, namely MN15-L and MN15, which were obtained by optimization against diverse databases. Time-dependent density functional theory, which is an extension of DFT to treat time-dependent problems and excited states. Furthermore, the review is a snapshot of a rapidly moving field, and—like Marcel Duchamp—we hope to convey progress in a stimulating way.},

doi = {10.1063/1.4963168},

journal = {Journal of Chemical Physics},

number = 13,

volume = 145,

place = {United States},

year = {2016},

month = {10}

}

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