Abstract: Eighteen polyolefin catalysts have been calculated using the density functional theory in the BP/DNP level. These compounds are classified into five groups with similar steric effect and different electronic effect. The Hirshfeld, Mulliken, and QEq charges and Fukui indexes of the central metals and HOMO and LUMO engeries of these compounds have been calculated. The QEq charge of the central metal and HOMO and LUMO energies have good correlation with the polymerization activity and can be used to predict polymerization activity of new designed catalysts. However, the Hirshfeld and Mulliken charges cannot correctly reflect the electronic effect change of the substituents. The Fukui index changes indecisively with substituent electronic effect and has inconspicuous correlation with the polymerization activities of these compounds.

Key words: polyolefin, substituent, electronic effect, density functional theory