ISSN:
0192-8651
Keywords:
olefin polymerization
;
Ziegler-Natta catalysis
;
quantum chemical methods
;
ethylene
;
TiH2CH3+
;
Chemistry
;
Theoretical, Physical and Computational Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Computer Science
Notes:
Insertion of ethylene into the Ti-methyl bond in TiH2CH+3 is chosen as a model reaction for investigating the performance of a range of contemporary quantum chemical models in polymerization studies. Basis set effects are investigated at the self-consistent-field level, covering Hartree-Fock, pure DFT, and hybrid DFT. In agreement with findings in part I of this study, the basis set sensitivity of ethylene is shown to introduce a bias in computed energetics, amounting to 2-3 kcal/mol when DZP bases are used to compute the overall heat of monomer insertion. The geometry of stationary points relevant to the insertion reaction is determined using hybrid density functional theory. Based on these structures, the energy profile of the insertion reaction is computed using a range of popular quantum chemical approximations. The methods include Hartree-Fock and Møller-Plesset (MP) perturbation theory up through the fourth order in spin-restricted, spin-unrestricted, and spin-projected formalisms. Furthermore, configuration-interaction-based methods are included, of which the top level method is singly and doubly excited coupled clusters with a perturbative estimate of the contribution from triply excited configurations added [CCSD(T)]. The performance of the methods just mentioned, as well as three pure density functional and three hybrid density functional methods, are compared with respect to “best” relative energies, defined through extrapolation of CCSD(T) correlation energies according to the PCI scheme of Siegbahn and coworkers. Even though the MP series show poor convergence, spin-projected MP2, as well as two pure DFT methods (BPW91, BP86) and PCI-78 based on the MCPF method, show similar and very good agreement with best relative energies for the insertion reaction. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 947-960, 1998
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
