Autor segons l'article: Sousa, Carmen; Llunell, Miquel; Domingo, Alex; de Graaf, Coen;
Departament: Química Física i Inorgànica
Autor/s de la URV: De Graaf, Cornelis
Paraules clau: State Spectroscopy Relaxation Molecule Dynamics Charge
Resum: 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.
Àrees temàtiques: 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
Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
ISSN: 14639076
Adreça de correu electrònic de l'autor: coen.degraaf@urv.cat
Identificador de l'autor: 0000-0001-8114-6658
Data d'alta del registre: 2024-09-07
Versió de l'article dipositat: info:eu-repo/semantics/acceptedVersion
URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
Referència a l'article segons font original: Physical Chemistry Chemical Physics. 20 (4): 2351-2355
Referència 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
Entitat: Universitat Rovira i Virgili
Any de publicació de la revista: 2018
Tipus de publicació: Journal Publications
Repositori URV