1. Coupling of distant parts of pyrrole molecule through virtual and resonant states
- Author
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P, Ragesh Kumar T, Nag, P., Ranković, M., Luxford, T. F. M., Kočišek, Mašín, Z., and Fedor, J.
- Subjects
Physics - Atomic Physics ,Physics - Chemical Physics - Abstract
We experimentally show that the N-H bond cleavage in 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. In order to interpret these 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 non-resonant $\sigma^*$ 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 it must happen on an ultrafast few-fs timescale.
- Published
- 2022