Author, as appears in the article.: López, J. ; Spivak, M; Arcisauskaite, V. ; McGrady, J. ; De Graaf, C.

Department: Química Física i Inorgànica

URV's Author/s: LÓPEZ FERNÁNDEZ, JAVIER; Spivak, M; Arcisauskaite, V. ; McGrady, J. ; DE GRAAF , CORNELIS

Keywords: trichromium electronic structure

Abstract: 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.

Research group: Química Quàntica

Thematic Areas: Chemistry Química Química

licence for use: https://creativecommons.org/licenses/by/3.0/es/

ISSN: 1477-9226

Author identifier: 0000-0003-0322-6796; ; ; ; 0000-0001-8114-6658

Record's date: 2018-02-28

Last page: 6211

Papper version: info:eu-repo/semantics/publishedVersion

Link to the original source: http://pubs.rsc.org/en/Content/ArticleLanding/2017/DT/C7DT01096F#!divAbstract

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

Article's DOI: 10.1039/C7DT01096F

Entity: Universitat Rovira i Virgili

Journal publication year: 2017

First page: 6202

Publication Type: Article Artículo Article