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

Department: Química Física i Inorgànica

URV's Author/s: De Graaf, Cornelis / López Fernández, Javier

Keywords: 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

Abstract: © 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.

Thematic Areas: 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

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

ISSN: 14779226

Author's mail: coen.degraaf@urv.cat javier.lopez@urv.cat

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

Record's date: 2023-02-26

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

Link to the original source: https://pubs.rsc.org/en/content/articlelanding/2017/dt/c7dt01096f

Licence document URL: http://repositori.urv.cat/ca/proteccio-de-dades/

Papper original source: Dalton Transactions. 46 (19): 6202-6211

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

Article's DOI: 10.1039/c7dt01096f

Entity: Universitat Rovira i Virgili

Journal publication year: 2017

Publication Type: Journal Publications