Abstract: This disclosure provides new methods for the design and development of ethylene polymerization catalysts, including Group 4 metallocene catalysts such as zirconocenes, which are based on an improved ability to adjust co-monomer incorporation into the polymer. Computational analyses with and without dispersion corrections revealed that designing catalyst scaffolds which induce stabilizing non-covalent dispersion type interactions with incoming ?-olefin co-monomers can be used to modulate co-monomer selectivity into the polyethylene chain. Demonstrated herein is a lack of correlation of computed ??G‡ values against experimental ??G‡ values when the dispersion correction (D3BJ) was disabled, and B3LYP was used in the absence of Grimme's D3 dispersion and Becke-Johnson (BJ) dampening, but a correlation of computed against experimental ??G‡ with B3LYP+D3BJ, which are used to design new catalyst scaffolds.

Abstract: This disclosure provides new methods for the design and development of ethylene polymerization catalysts, including Group 4 metallocene catalysts such as zirconocenes, which are based on an improved ability to adjust co-monomer incorporation into the polymer. Computational analyses with and without dispersion corrections revealed that designing catalyst scaffolds which induce stabilizing non-covalent dispersion type interactions with incoming ?-olefin co-monomers can be used to modulate co-monomer selectivity into the polyethylene chain. Demonstrated herein is a lack of correlation of computed ??G‡ values against experimental ??G‡ values when the dispersion correction (D3BJ) was disabled, and B3LYP was used in the absence of Grimme's D3 dispersion and Becke-Johnson (BJ) dampening, but a correlation of computed against experimental ??G‡ with B3LYP+D3BJ, which are used to design new catalyst scaffolds.