Articles producció científica> Química Física i Inorgànica

Theoretical evidence for the direct (MLCT)-M-3-HS deactivation in the light-induced spin crossover of Fe((II))-polypyridyl complexes

  • Identification data

    Identifier: imarina:6178098
    Authors:
    Sousa, CarmenLlunell, MiquelDomingo, Alexde Graaf, Coen
    Abstract:
    Spin-orbit couplings have been calculated in twenty snapshots of a molecular dynamics trajectory of [Fe(bpy)(3)](2+) to address the importance of geometrical distortions and second-order spin-orbit coupling on the intersystem crossing rate constants in the light-induced spin crossover process. It was found that the effective spin-orbit coupling between the (MLCT)-M-3 and T-5(2) state is much larger than the direct coupling in the symmetric structure, which opens the possibility of a direct (MLCT)-M-3-T-5(2) deactivation without the intervention of triplet metal-centered states. Based on the calculated deactivation times, we conclude that both the direct pathway and the one involving intermediate triplet states are active in the ultrafast population of the metastable HS state, bringing in agreement two experimental observations that advocate for either deactivation mechanism. This resolves a long-standing dispute about the deactivation mechanism of Fe((II))-polypyridyl complexes in particular, and about light-induced magnetism in transition metal complexes in general.
  • Others:

    Author, as appears in the article.: Sousa, Carmen; Llunell, Miquel; Domingo, Alex; de Graaf, Coen;
    Department: Química Física i Inorgànica
    URV's Author/s: De Graaf, Cornelis
    Keywords: State Spectroscopy Relaxation Molecule Dynamics Charge
    Abstract: Spin-orbit couplings have been calculated in twenty snapshots of a molecular dynamics trajectory of [Fe(bpy)(3)](2+) to address the importance of geometrical distortions and second-order spin-orbit coupling on the intersystem crossing rate constants in the light-induced spin crossover process. It was found that the effective spin-orbit coupling between the (MLCT)-M-3 and T-5(2) state is much larger than the direct coupling in the symmetric structure, which opens the possibility of a direct (MLCT)-M-3-T-5(2) deactivation without the intervention of triplet metal-centered states. Based on the calculated deactivation times, we conclude that both the direct pathway and the one involving intermediate triplet states are active in the ultrafast population of the metastable HS state, bringing in agreement two experimental observations that advocate for either deactivation mechanism. This resolves a long-standing dispute about the deactivation mechanism of Fe((II))-polypyridyl complexes in particular, and about light-induced magnetism in transition metal complexes in general.
    Thematic Areas: Química Physics, atomic, molecular & chemical Physics and astronomy (miscellaneous) Physics and astronomy (all) Physical and theoretical chemistry Odontología Medicina ii Medicina i Materiais Matemática / probabilidade e estatística Interdisciplinar Geociências General physics and astronomy General medicine Farmacia Ensino Engenharias iv Engenharias iii Engenharias ii Ciências biológicas ii Ciências biológicas i Ciências ambientais Ciências agrárias i Ciência de alimentos Ciência da computação Chemistry, physical Biotecnología Biodiversidade Astronomia / física
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 14639076
    Author's mail: coen.degraaf@urv.cat
    Author identifier: 0000-0001-8114-6658
    Record's date: 2024-09-07
    Papper version: info:eu-repo/semantics/acceptedVersion
    Link to the original source: https://pubs.rsc.org/en/content/articlelanding/2018/cp/c7cp08098k
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Papper original source: Physical Chemistry Chemical Physics. 20 (4): 2351-2355
    APA: Sousa, Carmen; Llunell, Miquel; Domingo, Alex; de Graaf, Coen; (2018). Theoretical evidence for the direct (MLCT)-M-3-HS deactivation in the light-induced spin crossover of Fe((II))-polypyridyl complexes. Physical Chemistry Chemical Physics, 20(4), 2351-2355. DOI: 10.1039/c7cp08098k
    Article's DOI: 10.1039/c7cp08098k
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2018
    Publication Type: Journal Publications
  • Keywords:

    Chemistry, Physical,Physical and Theoretical Chemistry,Physics and Astronomy (Miscellaneous),Physics, Atomic, Molecular & Chemical
    State
    Spectroscopy
    Relaxation
    Molecule
    Dynamics
    Charge
    Química
    Physics, atomic, molecular & chemical
    Physics and astronomy (miscellaneous)
    Physics and astronomy (all)
    Physical and theoretical chemistry
    Odontología
    Medicina ii
    Medicina i
    Materiais
    Matemática / probabilidade e estatística
    Interdisciplinar
    Geociências
    General physics and astronomy
    General medicine
    Farmacia
    Ensino
    Engenharias iv
    Engenharias iii
    Engenharias ii
    Ciências biológicas ii
    Ciências biológicas i
    Ciências ambientais
    Ciências agrárias i
    Ciência de alimentos
    Ciência da computação
    Chemistry, physical
    Biotecnología
    Biodiversidade
    Astronomia / física
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