Author, as appears in the article.: Alias-Rodriguez, Marc; de Graaf, Coen; Huix-Rotllant, Miquel;
Department: Química Física i Inorgànica
URV's Author/s: De Graaf, Cornelis
Keywords: Triplet States Spectroscopy Solvent dependence Phosphorescence Kinetics Fluorescence Benzophenone Aromatic ketones Acetophenone triplet states spectroscopy solvent dependence phosphorescence kinetics fluorescence benzophenone acetophenone
Abstract: 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.
Thematic Areas: 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
licence for use: https://creativecommons.org/licenses/by/3.0/es/
Author's mail: coen.degraaf@urv.cat
Author identifier: 0000-0001-8114-6658
Record's date: 2024-07-27
Papper version: info:eu-repo/semantics/acceptedVersion
Link to the original source: https://pubs.acs.org/doi/10.1021/jacs.1c07039
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Papper original source: Journal Of The American Chemical Society. 143 (51): 21474-21477
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
Article's DOI: 10.1021/jacs.1c07039
Entity: Universitat Rovira i Virgili
Journal publication year: 2021
Publication Type: Journal Publications