An optimized implementation of block-correlated coupled cluster theory based on the generalized valence bond wave function (GVB-BCCC) for the singlet ground state of strongly correlated systems is presented. The GVB-BCCC method with two-pair correlation (GVB-BCCC2b) or up to three-pair correlation (GVB-BCCC3b) will be the focus of this work. Three major techniques have been adopted to dramatically accelerate GVB-BCCC2b and GVB-BCCC3b calculations. First, the GVB-BCCC2b and GVB-BCCC3b codes are noticeably optimized by removing redundant calculations. Second, independent amplitudes are identified by constraining excited configurations to be pure singlet states and only independent amplitudes need to be solved. Third, an incremental updating scheme for the amplitudes in solving the GVB-BCCC equations is adopted. With these techniques, accurate GVB-BCCC3b calculations are now accessible for systems with relatively large active spaces (50 electrons in 50 orbitals) and GVB-BCCC2b calculations are affordable for systems with much larger active spaces. We have applied GVB-BCCC methods to investigate three typical kinds of systems: polyacenes, pentaprismane, and [Cu2O2]2+ isomers. For polyacenes, we demonstrate that GVB-BCCC3b can capture more than 94% of the total correlation energy even for 12-acene with 50 π electrons. For the potential energy curve of simultaneously stretching 15 C–C bonds in pentaprismane, our calculations show that the GVB-BCCC3b results are quite close to the results from the density matrix renormalization group (DMRG) over the whole range. For two dinuclear copper oxide isomers, their relative energy predicted by GVB-BCCC3b is also in good accord with the DMRG result. All calculations show that the inclusion of three-pair correlation in GVB-BCCC is critical for accurate descriptions of strongly correlated systems.

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.

The density functional theory (DFT) method was employed to investigate the nature of the copolymerization reaction of ethylene monomers and 2-methoxystyrene catalyzed by a palladium phosphine-sulfonate complex. The calculated results indicate that (1) the ethylene molecules prefer to coordinate with neutral phosphine-sulfonate Pd catalyst along the Pd–P side to generate an intermediate owning a cis-configuration, which indicate that the chain transfer proceeds from cis-3 but not trans-5. (2) Subsequently, the insertion of polar monomers in the chain propagation is easier than that of the ethylene monomer and adopts the 2,1 insertion pathway; meanwhile, the R-configuration pathway is more favorable than the S-configuration pathway in stage II. (3) After the polar monomer insertion, the β-H elimination pathway is easier than the ethylene insertion, which makes polar monomer insertion into the in-chain easier. This work revealed the mechanism of the copolymerization reaction of ethylene and 2-methoxystyrene catalyzed by a palladium phosphine-sulfonate complex, which could provide theoretical insights into the development of new transition-metal complexes for the copolymerization reaction.