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Ultrafast Intersystem Crossing in Xanthone from Wavepacket Dynamics

  • Identification data

    Identifier: imarina:9241830
    Authors:
    Alias-Rodriguez, Marcde Graaf, CoenHuix-Rotllant, Miquel
    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.
  • Others:

    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
  • Keywords:

    Biochemistry,Catalysis,Chemistry,Chemistry (Miscellaneous),Chemistry, Multidisciplinary,Colloid and Surface Chemistry
    Triplet
    States
    Spectroscopy
    Solvent dependence
    Phosphorescence
    Kinetics
    Fluorescence
    Benzophenone
    Aromatic ketones
    Acetophenone
    triplet
    states
    spectroscopy
    solvent dependence
    phosphorescence
    kinetics
    fluorescence
    benzophenone
    acetophenone
    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
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