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dc.contributor.authorFalivene, Laura
dc.contributor.authorBarone, Vincenzo
dc.contributor.authorTalarico, Giovanni
dc.date.accessioned2018-05-14T13:37:07Z
dc.date.available2018-05-14T13:37:07Z
dc.date.issued2018-04-24
dc.identifier.citationFalivene L, Barone V, Talarico G (2018) Unraveling the role of entropy in tuning unimolecular vs . bimolecular reaction rates: The case of olefin polymerization catalyzed by transition metals. Molecular Catalysis 452: 138–144. Available: http://dx.doi.org/10.1016/j.mcat.2018.04.012.
dc.identifier.issn2468-8231
dc.identifier.doi10.1016/j.mcat.2018.04.012
dc.identifier.urihttp://hdl.handle.net/10754/627871
dc.description.abstractOlefin 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.
dc.description.sponsorshipFunding 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.
dc.publisherElsevier BV
dc.relation.urlhttp://www.sciencedirect.com/science/article/pii/S2468823118301433
dc.subjectOlefin polymerization catalysis
dc.subjectBimolecular and unimolecular reactions
dc.subjectEntropy calculations
dc.subjectChain termination mechanisms
dc.subjectTransition metal catalysts
dc.titleUnraveling the role of entropy in tuning unimolecular vs . bimolecular reaction rates: The case of olefin polymerization catalyzed by transition metals
dc.typeArticle
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.identifier.journalMolecular Catalysis
dc.contributor.institutionScuola Normale Superiore, Piazza dei Cavalieri 7, 56125 Pisa, Italy
dc.contributor.institutionDipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia, 80126 Napoli, Italy
kaust.personFalivene, Laura
kaust.grant.numberKAUST-2017-C0854
dc.date.published-online2018-04-24
dc.date.published-print2018-06


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