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

  • Identification data

    Identifier: imarina:6389175
    Authors:
    Spivak MArcisauskaite VLópez XMcGrady JDe Graaf C
    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.
  • Others:

    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: 2024-10-26
    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: https://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
  • Keywords:

    Chemistry, Inorganic & Nuclear,Inorganic Chemistry
    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
    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
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