Olefin polymerization catalyzed by Group 4 transition metals is studied here as test case to reveal the entropy effects when bimolecular and unimolecular reactions are computed for processes occurring in solution. Catalytic systems characterized by different ligand frameworks, metal, and growing polymeric chain for which experimental data are available have been selected in order to validate the main approaches to entropy calculation. Applying the “standard” protocol results in a strong disagreement with the experimental results and the methods introducing a direct correction of the translational entropy term based on a single experimental parameter emerge as the most reliable. The general and powerful computational tool achieved in this study can represent a further step towards the “catalyst design” to control and predict the molecular mass of the resulting polymers.
Bibliographical noteKAUST Repository Item: Exported on 2020-10-01
Acknowledged KAUST grant number(s): KAUST-2017-C0854
Acknowledgements: Funding sources from the University of Naples Federico II (Ricerca Ateneo DR_409_2017). G.T. thanks the Kaust Catalysis Center of King Abdullah University of Science and Technology, Thuwal, Saudi Arabia, for the visiting contract KAUST-2017-C0854.