## Abstract

The recently developed multiconfiguration pair-density functional theory (MC-PDFT) combines multiconfiguration wave function theory with a density functional that depends on the on-top pair density of an electronic system. In an MC-PDFT calculation, there are two steps: a conventional multiconfiguration self-consistent-field (MCSCF) calculation and a post-MCSCF evaluation of the energy with an on-top density functional. In this work, we present the details of the MC-PDFT algorithm that avoids steeply scaling steps that are present in other post-self-consistent-field multireference calculations of dynamic correlation energy. We demonstrate the favorable scaling by considering systems of H_{2} molecules with active spaces of several different sizes. We then apply the MC-PDFT method to calculate the heterolytic dissociation enthalpy of ferrocene. We find that MC-PDFT yields results that are at least as accurate as complete active space second-order perturbation theory and are more stable with respect to basis set, but at a fraction of the cost in both time and memory.

Original language | English (US) |
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Article number | 034101 |

Journal | Journal of Chemical Physics |

Volume | 146 |

Issue number | 3 |

DOIs | |

State | Published - Jan 21 2017 |

### Bibliographical note

Funding Information:This work was supported in part by the National Science Foundation by Grant No. CHE14-64536.

Publisher Copyright:

© 2017 Author(s).