How the choice of a computational model could rule the chemical interpretation: The Ni(II) catalyzed ethylene dimerization as a case study

In this article, we present a critical study of the theoretical protocol used for the determination of the nickel(II) catalyzed ethylene dimerization mechanism, considered as a representative example of the various problems related to the modeling a catalytic cycle. The choice of an appropriate comp...

Full description

Saved in:
Bibliographic Details
Published in:Journal of computational chemistry 2010-04, Vol.31 (5), p.1053-1062
Main Authors: Tognetti, Vincent, Le Floch, Pascal, Adamo, Carlo
Format: Article
Language:English
Subjects:
Analytical chemistry
Atoms & subatomic particles
Catalysis
Chemical Sciences
DFT
ethylene dimerization
Nickel
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:In this article, we present a critical study of the theoretical protocol used for the determination of the nickel(II) catalyzed ethylene dimerization mechanism, considered as a representative example of the various problems related to the modeling a catalytic cycle. The choice of an appropriate computational procedure is indeed crucial for the validity of the conclusions that will be drawn from the computational process. The influence of the exchange-correlation functional on energetic profiles and geometries, the role of the basis set describing the metal atom, as well as the importance of the chosen molecular model, have been thus examined in details. From the obtained results, some general conclusions and guidelines are presented, which could constitute useful warnings in modeling homogenous catalysis. Besides, the database constituted by our high-level calculations can be used within benchmarking procedures to assess the performances of new computational methods based on density functional theory.
ISSN:0192-8651
1096-987X
DOI:10.1002/jcc.21392