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

Departamento: Química Física i Inorgànica

Autor/es de la URV: De Graaf, Cornelis / López Fernández, Javier

Palabras clave: Trichromium String complexes Self-consistent-field Quintuple bond Quantum-chemical calculations Local-spin-density Electronic structure Density-functional theory Cr-cr Bond-stretch isomerism Bimetallic systems 2nd-order perturbation-theory

Resumen: © 2017 The Royal Society of Chemistry. 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.

Áreas temáticas: Química Odontología Medicina ii Materiais Interdisciplinar Inorganic chemistry General medicine Farmacia Ensino Engenharias iv Engenharias iii Engenharias ii Engenharias i Ciências biológicas ii Ciências biológicas i Ciências ambientais Ciências agrárias i Chemistry, inorganic & nuclear Biotecnología Astronomia / física

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

ISSN: 14779226

Direcció de correo del autor: coen.degraaf@urv.cat javier.lopez@urv.cat

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

Fecha de alta del registro: 2023-02-26

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

Enlace a la fuente original: https://pubs.rsc.org/en/content/articlelanding/2017/dt/c7dt01096f

URL Documento de licencia: http://repositori.urv.cat/ca/proteccio-de-dades/

Referencia al articulo segun fuente origial: Dalton Transactions. 46 (19): 6202-6211

Referencia de l'ítem segons les normes APA: Spivak M; Arcisauskaite V; López X; McGrady J; De Graaf C (2017). A multiconfigurational approach to the electronic structure of trichromium extended metal atom chains. Dalton Transactions, 46(19), 6202-6211. DOI: 10.1039/C7DT01096F

DOI del artículo: 10.1039/c7dt01096f

Entidad: Universitat Rovira i Virgili

Año de publicación de la revista: 2017

Tipo de publicación: Journal Publications