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Comparison between alkalimetal and group 11 transition metal halide and hydride tetramers: Molecular structure and bonding

A comparison between alkalimetal (M = Li, Na, K, and Rb) and group 11 transition metal (M = Cu, Ag, and Au) (MX)inf4/inf tetramers with X = H, F, Cl, Br, and I has been carried out by means of the Amsterdam Density Functional software using density functional theory at the BP86/QZ4P level of theory and including relativistic effects through the ZORA approximation. We have obtained that, in the case of alkalimetals, the cubic isomer of Tinfd/inf geometry is more stable than the ring structure with Dinf4h/inf symmetry, whereas in the case of group 11 transition metal tetramers, the isomer with Dinf4h/inf symmetry (or Dinf2d/inf symmetry) is more stable than the Tinfd/inf form. To better understand the results obtained we have made energy decomposition analyses of the tetramerization energies. The results show that in alkalimetal halide and hydride tetramers, the cubic geometry is the most stable because the larger Pauli repulsion energies are compensated by the attractive electrostatic and orbital interaction terms. In the case of group 11 transition metal tetramers, the Dinf4h/inf/Dinf2d/inf geometry is more stable than the Tinfd/inf one due to the reduction of electrostatic stabilization and the dominant effect of the Pauli repulsion

We are grateful to the following organizations for financial support: the Ministerio de Ciencia e Innovacion (MICINN, project numbers CTQ2011-23156/BQU and CTQ2011-25086/BQU), the Generalitat de Catalunya (projects number 2009SGR528, 2009SGR637, and Xarxa de Referencia en Quimica Teorica i Computacional), and the FEDER fund (European Fund for Regional Development) for the grant UNGI08-4E-003. Excellent service by the Centre de Serveis Cientifics i Academics de Catalunya (CESCA) is gratefully acknowledged

© Journal of Physical Chemistry A, 2013, vol. 117, núm. 33, p. 8026-8034

American Chemical Society (ACS)

Autor: El Hamdi Lahfid, Majid
Solà i Puig, Miquel
Frenking, Gernot
Poater i Teixidor, Jordi
Data: 22 agost 2013
Resum: A comparison between alkalimetal (M = Li, Na, K, and Rb) and group 11 transition metal (M = Cu, Ag, and Au) (MX)inf4/inf tetramers with X = H, F, Cl, Br, and I has been carried out by means of the Amsterdam Density Functional software using density functional theory at the BP86/QZ4P level of theory and including relativistic effects through the ZORA approximation. We have obtained that, in the case of alkalimetals, the cubic isomer of Tinfd/inf geometry is more stable than the ring structure with Dinf4h/inf symmetry, whereas in the case of group 11 transition metal tetramers, the isomer with Dinf4h/inf symmetry (or Dinf2d/inf symmetry) is more stable than the Tinfd/inf form. To better understand the results obtained we have made energy decomposition analyses of the tetramerization energies. The results show that in alkalimetal halide and hydride tetramers, the cubic geometry is the most stable because the larger Pauli repulsion energies are compensated by the attractive electrostatic and orbital interaction terms. In the case of group 11 transition metal tetramers, the Dinf4h/inf/Dinf2d/inf geometry is more stable than the Tinfd/inf one due to the reduction of electrostatic stabilization and the dominant effect of the Pauli repulsion
We are grateful to the following organizations for financial support: the Ministerio de Ciencia e Innovacion (MICINN, project numbers CTQ2011-23156/BQU and CTQ2011-25086/BQU), the Generalitat de Catalunya (projects number 2009SGR528, 2009SGR637, and Xarxa de Referencia en Quimica Teorica i Computacional), and the FEDER fund (European Fund for Regional Development) for the grant UNGI08-4E-003. Excellent service by the Centre de Serveis Cientifics i Academics de Catalunya (CESCA) is gratefully acknowledged
Format: application/pdf
ISSN: 1089-5639 (versió paper)
1520-5215 (versió electrònica)
Accés al document: http://hdl.handle.net/10256/11396
Llenguatge: eng
Editor: American Chemical Society (ACS)
Col·lecció: MICINN/PN 2012-2014/CTQ2011-23156
MICINN/PN 2012-2014/CTQ2011-25086
AGAUR/2009-2014/2009 SGR-637
AGAUR/2009-2014/2009 SGR-528
Reproducció digital del document publicat a: http://dx.doi.org/10.1021/jp4051403
Articles publicats (D-Q)
És part de: © Journal of Physical Chemistry A, 2013, vol. 117, núm. 33, p. 8026-8034
Drets: Tots els drets reservats
Matèria: Funcional de densitat, Teoria del
Density functionals
Metalls de transició
Transition metals
Estructura molecular
Molecular structure
Títol: Comparison between alkalimetal and group 11 transition metal halide and hydride tetramers: Molecular structure and bonding
Tipus: info:eu-repo/semantics/article
Repositori: DUGiDocs

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