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An “inverse” harpoon mechanism
Electron-transfer reactions are ubiquitous in chemistry and biology. The electrons’ quantum nature allows their transfer across long distances. For example, in the well-known harpoon mechanism, electron transfer results in Coulombic attraction between initially neutral reactants, leading to a marked...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Association for the Advancement of Science
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9519053/ https://www.ncbi.nlm.nih.gov/pubmed/36170355 http://dx.doi.org/10.1126/sciadv.abq8084 |
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author | Gope, Krishnendu Livshits, Ester Bittner, Dror M. Baer, Roi Strasser, Daniel |
author_facet | Gope, Krishnendu Livshits, Ester Bittner, Dror M. Baer, Roi Strasser, Daniel |
author_sort | Gope, Krishnendu |
collection | PubMed |
description | Electron-transfer reactions are ubiquitous in chemistry and biology. The electrons’ quantum nature allows their transfer across long distances. For example, in the well-known harpoon mechanism, electron transfer results in Coulombic attraction between initially neutral reactants, leading to a marked increase in the reaction rate. Here, we present a different mechanism in which electron transfer from a neutral reactant to a multiply charged cation results in strong repulsion that encodes the electron-transfer distance in the kinetic energy release. Three-dimensional coincidence imaging allows to identify such “inverse” harpoon products, predicted by nonadiabatic molecular dynamics simulations to occur between H(2) and HCOH(2+) following double ionization of isolated methanol molecules. These dynamics are experimentally initiated by single-photon double ionization with ultrafast extreme ultraviolet pulses, produced by high-order harmonic generation. A detailed comparison of measured and simulated data indicates that while the relative probability of long-range electron-transfer events is correctly predicted, theory overestimates the electron-transfer distance. |
format | Online Article Text |
id | pubmed-9519053 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | American Association for the Advancement of Science |
record_format | MEDLINE/PubMed |
spelling | pubmed-95190532022-10-13 An “inverse” harpoon mechanism Gope, Krishnendu Livshits, Ester Bittner, Dror M. Baer, Roi Strasser, Daniel Sci Adv Physical and Materials Sciences Electron-transfer reactions are ubiquitous in chemistry and biology. The electrons’ quantum nature allows their transfer across long distances. For example, in the well-known harpoon mechanism, electron transfer results in Coulombic attraction between initially neutral reactants, leading to a marked increase in the reaction rate. Here, we present a different mechanism in which electron transfer from a neutral reactant to a multiply charged cation results in strong repulsion that encodes the electron-transfer distance in the kinetic energy release. Three-dimensional coincidence imaging allows to identify such “inverse” harpoon products, predicted by nonadiabatic molecular dynamics simulations to occur between H(2) and HCOH(2+) following double ionization of isolated methanol molecules. These dynamics are experimentally initiated by single-photon double ionization with ultrafast extreme ultraviolet pulses, produced by high-order harmonic generation. A detailed comparison of measured and simulated data indicates that while the relative probability of long-range electron-transfer events is correctly predicted, theory overestimates the electron-transfer distance. American Association for the Advancement of Science 2022-09-28 /pmc/articles/PMC9519053/ /pubmed/36170355 http://dx.doi.org/10.1126/sciadv.abq8084 Text en Copyright © 2022 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC). https://creativecommons.org/licenses/by-nc/4.0/This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial license (https://creativecommons.org/licenses/by-nc/4.0/) , which permits use, distribution, and reproduction in any medium, so long as the resultant use is not for commercial advantage and provided the original work is properly cited. |
spellingShingle | Physical and Materials Sciences Gope, Krishnendu Livshits, Ester Bittner, Dror M. Baer, Roi Strasser, Daniel An “inverse” harpoon mechanism |
title | An “inverse” harpoon mechanism |
title_full | An “inverse” harpoon mechanism |
title_fullStr | An “inverse” harpoon mechanism |
title_full_unstemmed | An “inverse” harpoon mechanism |
title_short | An “inverse” harpoon mechanism |
title_sort | “inverse” harpoon mechanism |
topic | Physical and Materials Sciences |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9519053/ https://www.ncbi.nlm.nih.gov/pubmed/36170355 http://dx.doi.org/10.1126/sciadv.abq8084 |
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