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Benchmark calculations of metal carbonyl cations: Relativistic vs. electron correlation effects

In this paper we present benchmark results for isoelectronic metal carbonyl complexes of the groups 11 and 12 of the periodic table. The focus is on the geometry, vibrational frequencies, bond dissociation energy and chemical bonding. The description of these complexes requires a good balance between electron correlation and relativistic effects. Our results demonstrate that the combination of the effective core potential and the MP2 method gives quantitative results for the first- and the second-row transition metal complexes and only qualitative agreement for the third-row complexes. In order to obtain quantitative results for the whole series the use of four-component or X2C methods is mandatory. The fourth-row transition metal carbonyl complexes from groups 11 and 12 have been studied for the first time. The metal-carbon bond strength pattern along the group is shown to be highly dependent on the correct description of the relativistic effects. Finally, the relativistic effects on the bonding are studied by means of electron density difference maps, the analysis of the bond critical points of the electron density and the mechanism for σ-donation and π-backdonation. Our analysis indicates that the fourth-row complexes exhibit a strong covalent character induced by relativistic effects

We would like to thank Dr Georg Eickerling and Prof. Scherer’s for providing a Mathematica script to analyze the topology of the density. Financial help has been furnished by the Polish Ministry of Science and Higher Education (project no. N N204 215634), the Spanish MICINN (project no. CTQ2011-23156/BQU and CTQ2011-23441/BQU) and by the FEDER fund (European Fund for Regional Development; grant UNGI08-4E-003). Financial support from the Generalitat de Catalunya (SGR637 and Xarxa de Referencia en Quimica Teorica i Computacional) is also acknowledged. E.M. acknowledges financial support from the EU under Marie Curie Career Integration grant (PCI09-GA-2011-294240) and the Beatriu de Pinos program from AGAUR for the postdoctoral grant (BP_B_00236). Most calculations reported in this paper have been performed in our (University of Szczecin) server SUN Fire X4400

© Physical Chemistry Chemical Physics, 2013, vol. 15, núm. 46, p. 20080-20090

Royal Society of Chemistry (RSC)

Author: Matito i Gras, Eduard
Salvador Sedano, Pedro
Styszyński, Jacek
Date: 2013
Abstract: In this paper we present benchmark results for isoelectronic metal carbonyl complexes of the groups 11 and 12 of the periodic table. The focus is on the geometry, vibrational frequencies, bond dissociation energy and chemical bonding. The description of these complexes requires a good balance between electron correlation and relativistic effects. Our results demonstrate that the combination of the effective core potential and the MP2 method gives quantitative results for the first- and the second-row transition metal complexes and only qualitative agreement for the third-row complexes. In order to obtain quantitative results for the whole series the use of four-component or X2C methods is mandatory. The fourth-row transition metal carbonyl complexes from groups 11 and 12 have been studied for the first time. The metal-carbon bond strength pattern along the group is shown to be highly dependent on the correct description of the relativistic effects. Finally, the relativistic effects on the bonding are studied by means of electron density difference maps, the analysis of the bond critical points of the electron density and the mechanism for σ-donation and π-backdonation. Our analysis indicates that the fourth-row complexes exhibit a strong covalent character induced by relativistic effects
We would like to thank Dr Georg Eickerling and Prof. Scherer’s for providing a Mathematica script to analyze the topology of the density. Financial help has been furnished by the Polish Ministry of Science and Higher Education (project no. N N204 215634), the Spanish MICINN (project no. CTQ2011-23156/BQU and CTQ2011-23441/BQU) and by the FEDER fund (European Fund for Regional Development; grant UNGI08-4E-003). Financial support from the Generalitat de Catalunya (SGR637 and Xarxa de Referencia en Quimica Teorica i Computacional) is also acknowledged. E.M. acknowledges financial support from the EU under Marie Curie Career Integration grant (PCI09-GA-2011-294240) and the Beatriu de Pinos program from AGAUR for the postdoctoral grant (BP_B_00236). Most calculations reported in this paper have been performed in our (University of Szczecin) server SUN Fire X4400
Format: application/pdf
ISSN: 1463-9076 (versió paper)
1463-9084 (versió electrònica)
Document access: http://hdl.handle.net/10256/11395
Language: eng
Publisher: Royal Society of Chemistry (RSC)
Collection: MICINN/PN 2012-2014/CTQ2011-23156
MICINN/PN 2012-2014/CTQ2011-23441
AGAUR/2009-2014/2009 SGR-637
AGAUR/2011-2013/BP_B_00236
Reproducció digital del document publicat a: http://dx.doi.org/10.1039/c3cp51798e
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/294240
Is part of: © Physical Chemistry Chemical Physics, 2013, vol. 15, núm. 46, p. 20080-20090
Rights: Tots els drets reservats
Subject: Funcional de densitat, Teoria del
Density functionals
Compostos carbonílics
Carbonyl compounds
Title: Benchmark calculations of metal carbonyl cations: Relativistic vs. electron correlation effects
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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