title: Modeling Transition Metal Reactions with Range-Separated Functionals.
abstract: The performance of range-separated functionals for the calculation of reaction profiles of organometallic compounds is considered. Sets of high-level computational results are used as reference data for the most part. The benchmark data include a number of reactions involving small molecules reacting with the Pd atom, PdCl(-), PdCl2, and a Ni atom, the reaction of a model Grubbs catalyst, and the ligand binding in a real Grubbs catalyst. Range-separated functionals are found to improve upon most standard local functionals especially if an optimized range-separation parameter is used. They do not represent an improvement upon the better-performed global hybrid functionals or a local functional that includes a larger number of adjustable parameters. Some unusual results for molecule-molecule interaction energies are observed and explained by a detailed analysis of the contributions to the bonding energies. The influence of range separation on the barriers and reaction energies is also investigated.
authors.affiliation: Department of Chemistry, University of Calgary , University Drive 2500, Calgary, AB T2N-1N4, Canada.
authors.forename: Michael
authors.initials: M
authors.lastname: Seth
authors.affiliation: Department of Chemistry, University of Calgary , University Drive 2500, Calgary, AB T2N-1N4, Canada.
authors.forename: Tom
authors.initials: T
authors.lastname: Ziegler
authors.affiliation: Mulliken Center for Theoretical Chemistry, Institute for Physical and Theoretical Chemistry, Universität Bonn , Beringstrasse 4, D-53115 Bonn, Germany.
authors.forename: Marc
authors.initials: M
authors.lastname: Steinmetz
authors.affiliation: Mulliken Center for Theoretical Chemistry, Institute for Physical and Theoretical Chemistry, Universität Bonn , Beringstrasse 4, D-53115 Bonn, Germany.
authors.forename: Stefan
authors.initials: S
authors.lastname: Grimme