Autor según el artículo: Alias-Rodriguez, Marc; de Graaf, Coen; Huix-Rotllant, Miquel;
Departamento: Química Física i Inorgànica
Autor/es de la URV: De Graaf, Cornelis
Palabras clave: Triplet States Spectroscopy Solvent dependence Phosphorescence Kinetics Fluorescence Benzophenone Aromatic ketones Acetophenone triplet states spectroscopy solvent dependence phosphorescence kinetics fluorescence benzophenone acetophenone
Resumen: Most aromatic ketones containing first-row elements undergo unexpectedly fast intersystem crossing in a few tens of picoseconds and a quantum yield close to unity. Among them, xanthone (9H-xanthen-9-one) possesses one of the fastest singlet- triplet rates of only similar to 1.5 ps. The exact mechanism of this unusually fast transition is still under debate. Here, we perform wavepacket dynamics of the photochemistry of xanthone in the gas phase and in polar solvents. We show that xanthone follows El-Sayed's rule for intersystem crossing. From the second singlet excited state, the mechanism is sequential: (i) an internal conversion between singlets 1 pi pi* -* 1n pi* (85 fs), (ii) an intersystem crossing 1n pi* -* 3 pi pi* (2.0 ps), and (iii) an internal conversion between triplets 3 pi pi* -* 3n pi* (602 fs). Each transfer finds its origin in a barrierless access to electronic state intersections. These intersections are close to minimum energy structures, allowing for efficient transitions from the initial singlet state to the triplets.
Áreas temáticas: Química Materiais Interdisciplinar General chemistry Farmacia Engenharias iv Engenharias iii Engenharias ii Colloid and surface chemistry Ciências biológicas ii Ciências biológicas i Ciências agrárias i Ciência de alimentos Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Chemistry Catalysis Biochemistry Astronomia / física
Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/
Direcció de correo del autor: coen.degraaf@urv.cat
Identificador del autor: 0000-0001-8114-6658
Fecha de alta del registro: 2024-07-27
Versión del articulo depositado: info:eu-repo/semantics/acceptedVersion
Enlace a la fuente original: https://pubs.acs.org/doi/10.1021/jacs.1c07039
URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
Referencia al articulo segun fuente origial: Journal Of The American Chemical Society. 143 (51): 21474-21477
Referencia de l'ítem segons les normes APA: Alias-Rodriguez, Marc; de Graaf, Coen; Huix-Rotllant, Miquel; (2021). Ultrafast Intersystem Crossing in Xanthone from Wavepacket Dynamics. Journal Of The American Chemical Society, 143(51), 21474-21477. DOI: 10.1021/jacs.1c07039
DOI del artículo: 10.1021/jacs.1c07039
Entidad: Universitat Rovira i Virgili
Año de publicación de la revista: 2021
Tipo de publicación: Journal Publications