An “inverse” harpoon mechanism


Gope, K. ; Livshits, E. ; Bittner, D. M. ; Baer, R. ; Strasser, D. An “inverse” harpoon mechanism. Science Advances 2022, 8 eabq8084.
An “inverse” harpoon mechanism

Date Published:

28 Sept 2022


Electron-transfer reactions are ubiquitous in chemistry and biology. The electrons quantum nature allows its transfer across long distances. In the well-known harpoon mechanism, electron-transfer results in Coulombic attraction between initially neutral reactants that leads to dramatic 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. 3D coincidence-imaging allows to identify such “inverse” harpoon products, predicted by non adiabatic molecular dynamics simulations to occur between H2 and HCOH2+ following double-ionization of isolated methanol molecules. 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.


Publisher: American Association for the Advancement of Science

Publisher's Version

Last updated on 10/16/2022