English

New approach for multiconfigurational Exchange-Correlation Functional

Chemical Physics 2018-02-15 v1 Quantum Physics

Abstract

New density functional theory approach based on a complete active space self-consistent field (CASSCF) reference function in Extended Koopmans' approximation is discussed. Recently, the number of generalizations of density functional theory based on a multiconfigurational CASSCF reference function with exact exchange (CASDFT) was introduced. It was shown by one of the authors (Dr. Gusarov) that such a theory could be formulated by introducing a special form of exchange-correlation potential. To take into account an active space and to avoid double counting of correlation energy the dependence from on-top pair density as a new variable was introduced. Unfortunately, this requires a deep review and reparametrization of existing functional expressions which lead to additional computational difficulties. The presented approach does not require introducing additional variables (like on-top pair density, and based on Extended Koopmans' theorem (EKT) approximation for multiconfigurational wave function within CASSCF method.

Keywords

Cite

@article{arxiv.1802.05265,
  title  = {New approach for multiconfigurational Exchange-Correlation Functional},
  author = {Sergey Gusarov and Yurii Dmitriev},
  journal= {arXiv preprint arXiv:1802.05265},
  year   = {2018}
}
R2 v1 2026-06-23T00:22:44.457Z