Combined quantum mechanics: Interatomic potential function investigation of rac-meso configurational stability and rotational transition in zirconocene-based Ziegler-Natta

The relative energetic stability of the "rac" and the "meso" rotational isomers of metallocene-based Ziegler-Natta (ZN) catalysts plays an important role in determining the structural, physical and chemical properties of synthesized polymers.Due to the large molecular size of these systems, ab initio calculations are often prohibitive. To circumvent this problem, weuse the QM-Pot approach, which treats the metal center and its surrounding atoms/ligands by quantum mechanics (QM), whereas the (organic) atoms/functional groups away from the metal center are described by an interatomic potential function (Pot). As a concrete example, we choose a commercially important zirconocene-based catalyst and compute: (1) the relative energies of the rac and meso structures; (2) the activation barrier for the rotational transition from one to the other; and (3) the effect: of the addition of organic functional groups on the above energies; Due to small mismatches between QM and Pot potential surfaces, one has to be careful in defining the QM cluster. In particular, larger QM clusters do not necessarily yield better results. Despite these difficulties, we show that it is possible to define a cluster for which the hybrid approach yields meaningful results when compared to full QM calculations.