Articles producció científica> Química Física i Inorgànica

A multiconfigurational approach to the electronic structure of trichromium extended metal atom chains

  • Dades identificatives

    Identificador: PC:3128
    Autors:
    López, J.Spivak, MArcisauskaite, V.McGrady, J.De Graaf, C.
    Resum:
    Filiació URV: SI
  • Altres:

    Autor segons l'article: López, J. ; Spivak, M; Arcisauskaite, V. ; McGrady, J. ; De Graaf, C.
    Departament: Química Física i Inorgànica
    Autor/s de la URV: LÓPEZ FERNÁNDEZ, JAVIER; Spivak, M; Arcisauskaite, V. ; McGrady, J. ; DE GRAAF , CORNELIS
    Paraules clau: trichromium electronic structure
    Resum: Density functional theory, Complete Active Space Self-Consistent Field (CASSCF) and perturbation theory (CASPT2) methodologies have been used to explore the electronic structure of a series of trichromium Extended Metal Atom Chains (EMACS) with different capping ligands. The study is motivated by the very different structural properties of these systems observed in X-ray experiments: the CN−-capped example has a symmetric Cr3 unit while for the NO3−-capped analogue the same unit has two very different Cr–Cr bond lengths. Density functional theory fails to locate an unsymmetric minimum for any of the systems studied, although the surface corresponding to the asymmetric stretch is very flat. CASPT2, in contrast, does locate an unsymmetric minimum only for the NO3−-capped system, although again the surface is very flat. We use the Generalized active space (GASSCF) technique and effective Hamiltonian theory to interrogate the multi-configurational wavefunctions of these systems, and show that the increase in the σ–σ* separation as the chain becomes unsymmetric plays a defining role in the stability of the ground state and its expansion in terms of configuration state functions.
    Grup de recerca: Química Quàntica
    Àrees temàtiques: Chemistry Química Química
    Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 1477-9226
    Identificador de l'autor: 0000-0003-0322-6796; ; ; ; 0000-0001-8114-6658
    Data d'alta del registre: 2018-02-28
    Pàgina final: 6211
    Versió de l'article dipositat: info:eu-repo/semantics/publishedVersion
    Enllaç font original: http://pubs.rsc.org/en/Content/ArticleLanding/2017/DT/C7DT01096F#!divAbstract
    Programa de finançament: altres; EPSRC; EP/K021435/1 european; COST Ac- tion ECOSTBio; CM1305 altres; XRQTC altres; Grupos Consolidados; 2014SGR199 plan; Excelencia; CTQ2014-51938-P
    URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
    DOI de l'article: 10.1039/C7DT01096F
    Entitat: Universitat Rovira i Virgili
    Any de publicació de la revista: 2017
    Pàgina inicial: 6202
    Tipus de publicació: Article Artículo Article
  • Paraules clau:

    Estructura electrònica
    trichromium
    electronic structure
    Chemistry
    Química
    Química
    1477-9226
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