Autor segons l'article: Alias-Rodriguez, Marc; de Graaf, Coen; Huix-Rotllant, Miquel;
Departament: Química Física i Inorgànica
Autor/s de la URV: De Graaf, Cornelis
Paraules clau: Triplet States Spectroscopy Solvent dependence Phosphorescence Kinetics Fluorescence Benzophenone Aromatic ketones Acetophenone triplet states spectroscopy solvent dependence phosphorescence kinetics fluorescence benzophenone acetophenone
Resum: 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.
Àrees temàtiques: 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
Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
Adreça de correu electrònic de l'autor: coen.degraaf@urv.cat
Identificador de l'autor: 0000-0001-8114-6658
Data d'alta del registre: 2023-02-23
Versió de l'article dipositat: info:eu-repo/semantics/acceptedVersion
Enllaç font original: https://pubs.acs.org/doi/10.1021/jacs.1c07039
URL Document de llicència: http://repositori.urv.cat/ca/proteccio-de-dades/
Referència a l'article segons font original: Journal Of The American Chemical Society. 143 (51): 21474-21477
Referència 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 de l'article: 10.1021/jacs.1c07039
Entitat: Universitat Rovira i Virgili
Any de publicació de la revista: 2021
Tipus de publicació: Journal Publications
Repositori URV