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
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
Entidad: Universitat Rovira i Virgili
Año de publicación de la revista: 2018
Tipo de publicación: Journal Publications
Repositori URV