## Abstract

This paper presents a new theory called multiconfiguration density coherence functional theory (MC-DCFT). This theory provides a new route to define density functionals for multiconfiguration wave functions, in particular by using the one-particle density matrix in the coordinate representation. The theory is illustrated by calculating the dissociation curve of four heteronuclear and homonuclear diatomic molecules, namely, H2, F2, N2, and HF, using density coherence functionals converted from PBE, BLYP, and PW91. By introducing two parameters in the converted density functionals, we are able to calculate bond dissociation energies of comparable accuracy as those calculated by multiconfiguration pair-density functional theory (MC-PDFT) and complete active space second-order perturbation theory (CASPT2). This demonstrates that it would be possible to build a successful multiconfiguration density functional theory based on density coherence.

Original language | English (US) |
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Pages (from-to) | 2775-2782 |

Number of pages | 8 |

Journal | Journal of Chemical Theory and Computation |

Volume | 17 |

Issue number | 5 |

DOIs | |

State | Published - May 11 2021 |

### Bibliographical note

Funding Information:This research was supported in part by the Air Force Office of Scientific Research under grant no. FA9550-20-1-0360.

Publisher Copyright:

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## PubMed: MeSH publication types

- Journal Article