Ab initio benchmark study for the oxidative addition of CH4 to Pd: importance of basis-set flexibility and polarization

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dc.contributor.author Theodoor De Jong, G.
dc.contributor.author Solà i Puig, Miquel
dc.contributor.author Visscher, Lucas T.
dc.contributor.author Bickelhaupt, Friedrich Matthias
dc.date.issued 2004
dc.identifier.citation Theodoor De Jong, G., Solà, M., Visscher, L., i Bickelhaupt, F.M. (2004). Ab initio benchmark study for the oxidative addition of CH4 to Pd: importance of basis-set flexibility and polarization. Journal of Chemical Physics, 121 (20), 9982-9992. Recuperat 28 març 2011,a http://link.aip.org/link/doi/10.1063/1.1792151
dc.identifier.issn 0021-9606 (versió paper)
dc.identifier.issn 1089-7690 (versió electrònica)
dc.identifier.uri http://hdl.handle.net/10256/3312
dc.description.abstract To obtain a state-of-the-art benchmark potential energy surface (PES) for the archetypal oxidative addition of the methane C-H bond to the palladium atom, we have explored this PES using a hierarchical series of ab initio methods (Hartree-Fock, second-order Møller-Plesset perturbation theory, fourth-order Møller-Plesset perturbation theory with single, double and quadruple excitations, coupled cluster theory with single and double excitations (CCSD), and with triple excitations treated perturbatively [CCSD(T)]) and hybrid density functional theory using the B3LYP functional, in combination with a hierarchical series of ten Gaussian-type basis sets, up to g polarization. Relativistic effects are taken into account either through a relativistic effective core potential for palladium or through a full four-component all-electron approach. Counterpoise corrected relative energies of stationary points are converged to within 0.1-0.2 kcal/mol as a function of the basis-set size. Our best estimate of kinetic and thermodynamic parameters is -8.1 (-8.3) kcal/mol for the formation of the reactant complex, 5.8 (3.1) kcal/mol for the activation energy relative to the separate reactants, and 0.8 (-1.2) kcal/mol for the reaction energy (zero-point vibrational energy-corrected values in parentheses). This agrees well with available experimental data. Our work highlights the importance of sufficient higher angular momentum polarization functions, f and g, for correctly describing metal-d-electron correlation and, thus, for obtaining reliable relative energies. We show that standard basis sets, such as LANL2DZ+ 1f for palladium, are not sufficiently polarized for this purpose and lead to erroneous CCSD(T) results. B3LYP is associated with smaller basis set superposition errors and shows faster convergence with basis-set size but yields relative energies (in particular, a reaction barrier) that are ca. 3.5 kcal/mol higher than the corresponding CCSD(T) values
dc.format.mimetype application/pdf
dc.language.iso eng
dc.publisher American Institute of Physics
dc.relation.isformatof Reproducció digital del document publicat a: http://dx.doi.org/10.1063/1.1792151
dc.relation.ispartof © Journal of Chemical Physics, 2004, vol. 121, núm. 20, p. 9982-9992
dc.relation.ispartofseries Articles publicats (D-Q)
dc.rights Tots els drets reservats
dc.subject Anàlisi d'error (Matemàtica)
dc.subject Aproximació, Teoria de l'
dc.subject Enllaços químics
dc.subject Funcional de densitat, Teoria del
dc.subject Metà
dc.subject Pal·ladi
dc.subject Pertorbació (Matemàtica)
dc.subject Polarització (Electricitat)
dc.subject Reaccions d'addició
dc.subject Addition reactions
dc.subject Approximation theory
dc.subject Chemical bonds
dc.subject Density functionals
dc.subject Error analysis (Mathematics)
dc.subject Methane
dc.subject Palladium
dc.subject Perturbation (Mathematics)
dc.subject Polarization (Electricity)
dc.title Ab initio benchmark study for the oxidative addition of CH4 to Pd: importance of basis-set flexibility and polarization
dc.type info:eu-repo/semantics/article
dc.identifier.doi http://dx.doi.org/10.1063/1.1792151

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