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

  • Datos identificativos

    Identificador: imarina:6178098
    Autores:
    Sousa, CarmenLlunell, MiquelDomingo, Alexde Graaf, Coen
    Resumen:
    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.
  • Otros:

    Autor según el artículo: Sousa, Carmen; Llunell, Miquel; Domingo, Alex; de Graaf, Coen;
    Departamento: Química Física i Inorgànica
    Autor/es de la URV: De Graaf, Cornelis
    Palabras clave: State Spectroscopy Relaxation Molecule Dynamics Charge
    Resumen: 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.
    Áreas temáticas: 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
    Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 14639076
    Direcció de correo del autor: coen.degraaf@urv.cat
    Identificador del autor: 0000-0001-8114-6658
    Fecha de alta del registro: 2024-09-07
    Versión del articulo depositado: info:eu-repo/semantics/acceptedVersion
    Enlace a la fuente original: https://pubs.rsc.org/en/content/articlelanding/2018/cp/c7cp08098k
    URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
    Referencia al articulo segun fuente origial: Physical Chemistry Chemical Physics. 20 (4): 2351-2355
    Referencia de l'ítem segons les normes 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
    DOI del artículo: 10.1039/c7cp08098k
    Entidad: Universitat Rovira i Virgili
    Año de publicación de la revista: 2018
    Tipo de publicación: Journal Publications
  • Palabras clave:

    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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