Few-femtosecond electron transfer dynamics in photoionized donor-π-acceptor molecules.

Autor: Vismarra F; Department of Physics, Politecnico di Milano, Milan, Italy.; Institute for Photonics and Nanotechnologies, IFN-CNR, Milan, Italy., Fernández-Villoria F; Instituto Madrileño de Estudios Avanzados en Nanociencia, Madrid, Spain.; Departamento de Química, Universidad Autónoma de Madrid, Madrid, Spain., Mocci D; Department of Physics, Politecnico di Milano, Milan, Italy., González-Vázquez J; Departamento de Química, Universidad Autónoma de Madrid, Madrid, Spain., Wu Y; Department of Physics, Politecnico di Milano, Milan, Italy.; Institute for Photonics and Nanotechnologies, IFN-CNR, Milan, Italy., Colaizzi L; Department of Physics, Politecnico di Milano, Milan, Italy., Holzmeier F; imec, Leuven, Belgium., Delgado J; Instituto Madrileño de Estudios Avanzados en Nanociencia, Madrid, Spain.; Departamento de Química, Universidad Autónoma de Madrid, Madrid, Spain., Santos J; Instituto Madrileño de Estudios Avanzados en Nanociencia, Madrid, Spain.; Departamento de Química Orgánica I, Universidad Complutense de Madrid, Madrid, Spain., Bañares L; Instituto Madrileño de Estudios Avanzados en Nanociencia, Madrid, Spain.; Departamento de Química Física, Universidad Complutense de Madrid, Madrid, Spain., Carlini L; Istituto di Struttura della Materia-CNR (ISM-CNR), Rome, Italy., Castrovilli MC; Istituto di Struttura della Materia-CNR (ISM-CNR), Rome, Italy., Bolognesi P; Istituto di Struttura della Materia-CNR (ISM-CNR), Rome, Italy., Richter R; Sincrotrone Trieste, Area Science Park, Basovizza, Trieste, Italy., Avaldi L; Istituto di Struttura della Materia-CNR (ISM-CNR), Rome, Italy., Palacios A; Departamento de Química, Universidad Autónoma de Madrid, Madrid, Spain., Lucchini M; Department of Physics, Politecnico di Milano, Milan, Italy.; Institute for Photonics and Nanotechnologies, IFN-CNR, Milan, Italy., Reduzzi M; Department of Physics, Politecnico di Milano, Milan, Italy., Borrego-Varillas R; Institute for Photonics and Nanotechnologies, IFN-CNR, Milan, Italy. rocio.borregovarillas@cnr.it., Martín N; Instituto Madrileño de Estudios Avanzados en Nanociencia, Madrid, Spain.; Departamento de Química Orgánica I, Universidad Complutense de Madrid, Madrid, Spain., Martín F; Instituto Madrileño de Estudios Avanzados en Nanociencia, Madrid, Spain. fernando.martin@uam.es.; Departamento de Química, Universidad Autónoma de Madrid, Madrid, Spain. fernando.martin@uam.es., Nisoli M; Department of Physics, Politecnico di Milano, Milan, Italy. mauro.nisoli@polimi.it.; Institute for Photonics and Nanotechnologies, IFN-CNR, Milan, Italy. mauro.nisoli@polimi.it.
Jazyk: angličtina
Zdroj: Nature chemistry [Nat Chem] 2024 Sep 25. Date of Electronic Publication: 2024 Sep 25.
DOI: 10.1038/s41557-024-01620-y
Abstrakt: The exposure of molecules to attosecond extreme-ultraviolet (XUV) pulses offers a unique opportunity to study the early stages of coupled electron-nuclear dynamics in which the role played by the different degrees of freedom is beyond standard chemical intuition. We investigate, both experimentally and theoretically, the first steps of charge-transfer processes initiated by prompt ionization in prototype donor-π-acceptor molecules, namely nitroanilines. Time-resolved measurement of this process is performed by combining attosecond XUV-pump/few-femtosecond infrared-probe spectroscopy with advanced many-body quantum chemistry calculations. We show that a concerted nuclear and electronic motion drives electron transfer from the donor group on a sub-10-fs timescale. This is followed by a sub-30-fs relaxation process due to the probing of the continuously spreading nuclear wave packet in the excited electronic states of the molecular cation. These findings shed light on the role played by electron-nuclear coupling in donor-π-acceptor systems in response to photoionization.
(© 2024. The Author(s).)
Databáze: MEDLINE
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