### Abstract

Self-interaction is a central problem for the accuracy of density-functional approximations in describing the electronic structure of atoms and molecules. In this work, we discuss the different types of self-interaction errors commonly encountered in density-functional calculations, providing precise definitions for each of them. Based upon these definitions, we derive an orbital-dependent density-functional method, called the Koopmans-compliant approach, which simultaneously corrects the different self-interaction errors, by enforcing piecewise linearity with respect to fractional particle counts and by imposing the correct asymptotic behavior of the one-electron potential in approximate energy functionals. We illustrate the very good performance of this new method in predicting the electronic properties of atoms and molecules, while preserving or improving the prediction of total energies and equilibrium geometries. These results highlight the accuracy and efficiency of Koopmans-compliant functionals as an attractive solution to the self-interaction problem.

Original language | English (US) |
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Title of host publication | Advances In Atomic, Molecular, and Optical Physics, 2015 |

Editors | Chun C. Lin, Ennio Arimondo, Susanne F. Yelin |

Publisher | Academic Press Inc. |

Pages | 105-127 |

Number of pages | 23 |

ISBN (Print) | 9780128021279 |

DOIs | |

State | Published - Jan 1 2015 |

### Publication series

Name | Advances in Atomic, Molecular and Optical Physics |
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Volume | 64 |

ISSN (Print) | 1049-250X |

### Fingerprint

### All Science Journal Classification (ASJC) codes

- Statistical and Nonlinear Physics
- Electronic, Optical and Magnetic Materials

### Cite this

*Advances In Atomic, Molecular, and Optical Physics, 2015*(pp. 105-127). (Advances in Atomic, Molecular and Optical Physics; Vol. 64). Academic Press Inc.. https://doi.org/10.1016/bs.aamop.2015.06.008

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*Advances In Atomic, Molecular, and Optical Physics, 2015.*Advances in Atomic, Molecular and Optical Physics, vol. 64, Academic Press Inc., pp. 105-127. https://doi.org/10.1016/bs.aamop.2015.06.008

**Koopmans-Compliant Self-Interaction Corrections.** / Poilvert, Nicolas; Borghi, Giovanni; Nguyen, Ngoc Linh; Keilbart, Nathan Daniel; Wang, Kevin; Dabo, Ismaila.

Research output: Chapter in Book/Report/Conference proceeding › Conference contribution

TY - GEN

T1 - Koopmans-Compliant Self-Interaction Corrections

AU - Poilvert, Nicolas

AU - Borghi, Giovanni

AU - Nguyen, Ngoc Linh

AU - Keilbart, Nathan Daniel

AU - Wang, Kevin

AU - Dabo, Ismaila

PY - 2015/1/1

Y1 - 2015/1/1

N2 - Self-interaction is a central problem for the accuracy of density-functional approximations in describing the electronic structure of atoms and molecules. In this work, we discuss the different types of self-interaction errors commonly encountered in density-functional calculations, providing precise definitions for each of them. Based upon these definitions, we derive an orbital-dependent density-functional method, called the Koopmans-compliant approach, which simultaneously corrects the different self-interaction errors, by enforcing piecewise linearity with respect to fractional particle counts and by imposing the correct asymptotic behavior of the one-electron potential in approximate energy functionals. We illustrate the very good performance of this new method in predicting the electronic properties of atoms and molecules, while preserving or improving the prediction of total energies and equilibrium geometries. These results highlight the accuracy and efficiency of Koopmans-compliant functionals as an attractive solution to the self-interaction problem.

AB - Self-interaction is a central problem for the accuracy of density-functional approximations in describing the electronic structure of atoms and molecules. In this work, we discuss the different types of self-interaction errors commonly encountered in density-functional calculations, providing precise definitions for each of them. Based upon these definitions, we derive an orbital-dependent density-functional method, called the Koopmans-compliant approach, which simultaneously corrects the different self-interaction errors, by enforcing piecewise linearity with respect to fractional particle counts and by imposing the correct asymptotic behavior of the one-electron potential in approximate energy functionals. We illustrate the very good performance of this new method in predicting the electronic properties of atoms and molecules, while preserving or improving the prediction of total energies and equilibrium geometries. These results highlight the accuracy and efficiency of Koopmans-compliant functionals as an attractive solution to the self-interaction problem.

UR - http://www.scopus.com/inward/record.url?scp=84939818341&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84939818341&partnerID=8YFLogxK

U2 - 10.1016/bs.aamop.2015.06.008

DO - 10.1016/bs.aamop.2015.06.008

M3 - Conference contribution

AN - SCOPUS:84939818341

SN - 9780128021279

T3 - Advances in Atomic, Molecular and Optical Physics

SP - 105

EP - 127

BT - Advances In Atomic, Molecular, and Optical Physics, 2015

A2 - Lin, Chun C.

A2 - Arimondo, Ennio

A2 - Yelin, Susanne F.

PB - Academic Press Inc.

ER -