Quantum Chemical Topology of the Electron Localization Function in the Field of Attosecond Electron Dynamics

• Published in: The journal of physical chemistry letters 2018-02, Vol.9 (4), p.844-850
• Main Authors: Parise, Angela, Alvarez-Ibarra, Aurelio, Wu, Xiaojing, Zhao, Xiaodong, Pilmé, Julien, de la Lande, Aurélien
• Format: Article
• Language: English
• Subjects: Chemical Sciences
• ISSN: 1948-7185; 1948-7185
• DOI: 10.1021/acs.jpclett.7b03379

We report original analyses of attosecond electron dynamics of molecules subject to collisions by high energy charged particles based on Real-Time Time-Dependent-Density-Functional-Theory simulations coupled to Topological Analyses of the Electron Localization Function (TA-TD-ELF). We investigate irradiation of water and guanine. TA-TD-ELF enables qualitative and quantitative characterizations of bond breaking and formation, of charge migration within topological basins, or of electron attachment to the colliding particle. Whereas the Lewis-VSEPR structure of gas phase water is blown out within a few attoseconds after collision, that of guanine is far more robust and reconstitutes rapidly after impact even though the molecule remains electronically excited. This difference is accounted by the presence of the electron bath surrounding the impact point which enables energy relaxation within the molecule. Our approach should stimulate future studies to unravel the early steps following irradiation of various types of systems (isolated molecules, biomolecules, nanoclusters, solids, etc.) and is also readily applicable to irradiation by photons of various energies.