Distant Symmetry Control in Electron-Induced Bond Cleavage

Article

Distant Symmetry Control in Electron-Induced Bond Cleavage

Kumar, T. P. R.; Nag, P.; Rankovič, M.; Luxford, T. F. M.; Kočišek, J.; Mašín, Z.; Fedor, J.

J. Phys. Chem. Lett. 13(48), 7 (2022)

Abstract

We experimentally show that N-H bond cleavage in the pyrrole molecule following resonant electron attachment is allowed and controlled by the motion of the atoms which are not dissociating, namely, of the carbon-attached hydrogen atoms. We use this fact to steer the efficiency of this bond cleavage. In order to interpret the experimental findings, we have developed a method for locating all resonant and virtual states of an electron-molecule system in the complex plane, based on all-electron R-matrix scattering calculations. Mapping these as a function of molecular geometry allows us to separate two contributing dissociation mechanisms: a pi*resonance formation inducing strong bending deformations and a nonresonant sigma* mechanism originating in a virtual state. The coupling between the two mechanisms is enabled by the out-of-plane motion of the C-H bonds, and we show that it must happen on an ultrafast (few fs) time scale.

Institute authors

Mašín, Zdeněk

Supported by

GACR 20-15548Y — New mechanisms of damage of DNA driven by electrons and ultraviolet light
Primus/20/SCI/003 — New mechanisms of damage of DNA driven by electrons and ultraviolet light

BibTeX

@article{UTF927,
  author        = {Kumar, T. P. R. and Nag, P. and Rankovič, M. and Luxford, T. F. M. and Kočišek, J. and Mašín, Z. and Fedor, J.},
  title         = {{Distant Symmetry Control in Electron-Induced Bond Cleavage}},
  journal       = {J. Phys. Chem. Lett.},
  volume        = {13},
  number        = {48},
  pages         = {7},
  year          = {2022},
  month         = {11},
  doi           = {10.1021/acs.jpclett.2c03096},
}