title: A minimalistic approach to static and dynamic electron correlations: Amending generalized valence bond method with extended random phase approximation correlation correction.
abstract: A perfect-pairing generalized valence bond (GVB) approximation is known to be one of the simplest approximations, which allows one to capture the essence of static correlation in molecular systems. In spite of its attractive feature of being relatively computationally efficient, this approximation misses a large portion of dynamic correlation and does not offer sufficient accuracy to be generally useful for studying electronic structure of molecules. We propose to correct the GVB model and alleviate some of its deficiencies by amending it with the correlation energy correction derived from the recently formulated extended random phase approximation (ERPA). On the examples of systems of diverse electronic structures, we show that the resulting ERPA-GVB method greatly improves upon the GVB model. ERPA-GVB recovers most of the electron correlation and it yields energy barrier heights of excellent accuracy. Thanks to a balanced treatment of static and dynamic correlation, ERPA-GVB stays reliable when one moves from systems dominated by dynamic electron correlation to those for which the static correlation comes into play.
authors.affiliation: Institute of Applied Radiation Chemistry, Lodz University of Technology, ul. Wroblewskiego 15, 93-590 Lodz, Poland.
authors.forename: Koushik
authors.initials: K
authors.lastname: Chatterjee
authors.affiliation: Institute of Physics, Lodz University of Technology, ul. Wolczanska 219, 90-924 Lodz, Poland.
authors.forename: Ewa
authors.initials: E
authors.lastname: Pastorczak
authors.affiliation: Institute of Applied Radiation Chemistry, Lodz University of Technology, ul. Wroblewskiego 15, 93-590 Lodz, Poland.
authors.forename: Konrad
authors.initials: K
authors.lastname: Jawulski
authors.affiliation: Institute of Physics, Lodz University of Technology, ul. Wolczanska 219, 90-924 Lodz, Poland.
authors.forename: Katarzyna
authors.initials: K
authors.lastname: Pernal