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Ministerio de Ciencia e Innovaci贸n (Espanya)
Generalitat de Catalunya. Ag猫ncia de Gesti贸 d鈥橝juts Universitaris i de Recerca |
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El Hamdi Lahfid, Majid
Sol脿 i Puig, Miquel Frenking, Gernot Poater i Teixidor, Jordi |
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2013 August 22 | |
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 |
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application/pdf | |
http://hdl.handle.net/10256/11396 | |
eng | |
American Chemical Society (ACS) | |
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp4051403 info:eu-repo/semantics/altIdentifier/issn/1089-5639 info:eu-repo/semantics/altIdentifier/eissn/1520-5215 info:eu-repo/grantAgreement/MICINN//CTQ2011-23156/ES/AVANCES EN CATALISIS Y AROMATICIDAD/ info:eu-repo/grantAgreement/MICINN//CTQ2011-25086/ES/MODELIZACION MULTIESCALAR EN (BIO)QUIMICA/ AGAUR/2009-2014/2009 SGR-637 AGAUR/2009-2014/2009 SGR-528 |
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Tots els drets reservats | |
Funcional de densitat, Teoria del
Density functionals Metalls de transici贸 Transition metals Estructura molecular Molecular structure |
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Comparison between alkalimetal and group 11 transition metal halide and hydride tetramers: Molecular structure and bonding | |
info:eu-repo/semantics/article | |
DUGiDocs |