Distant Symmetry Control in Electron-Induced Bond Cleavage

0566064 - ÚFCH JH 2023 RIV US eng J - Článek v odborném periodiku
Kumar, Ragesh Thelakkadan Puthiyaveettil - Nag, Pamir - Ranković, Miloš - Luxford, Thomas Frederick Murray - Kočišek, Jaroslav - Mašín, Z. - Fedor, Juraj
Distant Symmetry Control in Electron-Induced Bond Cleavage.
Journal of Physical Chemistry Letters. Roč. 13, č. 48 (2022), s. 11136-11142. ISSN 1948-7185
Grant CEP: GA ČR(CZ) GX21-26601X
Výzkumná infrastruktura: e-INFRA CZ - 90140; IT4Innovations - 90070
Institucionální podpora: RVO:61388955
Klíčová slova: Bond cleavage * Electrical energy * Resonance structures
Obor OECD: Physical chemistry
Impakt faktor: 5.7, rok: 2022
Způsob publikování: Omezený přístup

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.
Trvalý link: https://hdl.handle.net/11104/0337503