Equation-of-Motion Block-Correlated Coupled Cluster Method for Excited Electronic States of Strongly Correlated Systems.

J Phys Chem Lett

Key Laboratory of Mesoscopic Chemistry of Ministry of Education, New Cornerstone Science Laboratory, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, People's Republic of China.

Published: August 2023

An equation-of-motion block-correlated coupled cluster method based on the generalized valence bond wave function (EOM-GVB-BCCC) is proposed to describe low-lying excited states for strongly correlated systems. The EOM-GVB-BCCC2b method with up to two-pair correlation has been implemented and tested for a few strongly correlated systems. For a water hexamer with stretched O-H bonds, which is beyond the capability of the CASSCF method, EOM-GVB-BCCC2b provides very close results as the density matrix renormalization group (DMRG). For four conjugated diradical species with triplet ground states, we found that their vertical S-T gaps from EOM-GVB-BCCC2b are also quite consistent with the DMRG results. This new method is expected to be a promising theoretical tool for describing the low-lying excited states of strongly correlated systems with large active spaces.

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http://dx.doi.org/10.1021/acs.jpclett.3c01474DOI Listing

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