2018/02/14 by Sergey Gusarov, Gusarov, Sergey, Yurii Dmitriev +1
Chemistry · Physics and Astronomy · #Advanced Chemical Physics Studies #Chemical Physics (physics.chem-ph) #FOS: Physical sciences #Molecular spectroscopy and chirality #Quantum Physics (quant-ph) #Spectroscopy and Quantum Chemical Studies
paper · pdf · doi:10.48550/arxiv.1802.05265
openalex publication_date 2018/02/14 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
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.