Autor según el artículo: López, J. ; Spivak, M; Arcisauskaite, V. ; McGrady, J. ; De Graaf, C.

Departamento: Química Física i Inorgànica

Autor/es de la URV: LÓPEZ FERNÁNDEZ, JAVIER; Spivak, M; Arcisauskaite, V. ; McGrady, J. ; DE GRAAF , CORNELIS

Palabras clave: trichromium electronic structure

Resumen: 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.

Grupo de investigación: Química Quàntica

Áreas temáticas: Chemistry Química Química

Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/

ISSN: 1477-9226

Identificador del autor: 0000-0003-0322-6796; ; ; ; 0000-0001-8114-6658

Fecha de alta del registro: 2018-02-28

Página final: 6211

Versión del articulo depositado: info:eu-repo/semantics/publishedVersion

Enlace a la fuente original: http://pubs.rsc.org/en/Content/ArticleLanding/2017/DT/C7DT01096F#!divAbstract

Programa de financiación: altres; EPSRC; EP/K021435/1 european; COST Ac- tion ECOSTBio; CM1305 altres; XRQTC altres; Grupos Consolidados; 2014SGR199 plan; Excelencia; CTQ2014-51938-P

DOI del artículo: 10.1039/C7DT01096F

Entidad: Universitat Rovira i Virgili

Año de publicación de la revista: 2017

Página inicial: 6202

Tipo de publicación: Article Artículo Article