In my presentation, I will focus on ab initio simulations of novel electron and charge transfer processes identified recently in hydrogen bonded systems. Highly excited molecules relax dominantly by autoionization processes, Auger decay being the most familiar example. Autoionization was considered to be dominantly on-site process, i.e., the excited molecule also ionizes. Recently, various non-local ionization processes such as Intermolecular Coulomb Decay (ICD) or Electron Transfer Mediated Decay (ETMD) were identified.[1] Despite the ultrafast nature of these processes, electron and nuclear dynamics are strongly entangled, leading to a whole plethora of new channels in condensed phase.[2,3] Spectroscopic signatures of these new relaxation pathways and their possible applications as a new spectroscopy tools in liquid phase will be discussed in my talk. I will argue that liquid phase Auger spectra convey invaluable information on hydrogen bonding structure of liquids or molecular speciation when combined with theoretical analysis. I will further discuss molecular simulations of ultrafast relaxation processes following the interaction of molecules and liquids with high-energy radiation. Results obtained with methods of quantum dynamics, non-adiabatic semiclassical dynamics and real time density functional theory will be shown. These results update the view on the first few femtoseconds in radiation chemistry. REFERENCES [1] T. Jahnke, Interatomic and intermolecular Coulombic decay: the coming of age story. J. Phys. B., 48, 082001, (2015). [2] S. Thürmer, M. Ončák, N. Ottosson, R. Seidel, U. Hergenhahn, S. E. Bradforth, P. Slavíček, B. Winter, On the nature and origin of dicationic charge-separated species formed in liquid water on X-ray irradiation. Nature Chemistry 5, 590 (2013). [3] P. Slavíček, B. Winter, L. S. Cederbaum, N. V. Kryzhevoi. Proton-Transfer Mediated Enhancement of Nonlocal Electronic Relaxation Processes in X-ray Irradiated Liquid Water, J. Am. Chem. Soc. 136, 18170 (2014). The work was supported by Czech Science foundation (project number 13-34168S) and by MSMT CR, project KONTAKT II.

Novel relaxation pathways in liquid phase: Concerted electronic and nuclear motion

251st National Meeting (2016)

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