Reactivity toward low-energy electrons (LEE) has been hypothesized as a cause of radio-modifying properties for various molecules. LEE's transient nature, however, prevents the establishment of clear links between initial processes at the sub-ps time scale and the final products of radiolysis. Here, such links are explored for the radio-modifying compound RRx-001 (1-bromoacetyl-3,3-dinitroazetidine). Picosecond pulse radiolysis demonstrates the high scavenging capacity of the molecule for secondary quasi-free and solvated electrons forming stable parent anions confirmed by studies of microsolvated RRx-001 in clusters. The anions decay either via auto-detachment of an electron or dissociate involving hydrogen transfer from solvent, resulting in NO2 and 1-(bromoacetyl)-3-nitroazetidine. Surprisingly, no Br dissociation is observed despite its high electron affinity. We assign this behavior to the "inaccessibility" of sigma virtual states for electrons in the solvent, which can be of a general nature.

Center for Molecular Biosciences Innsbruck Universität Innsbruck Technikerstraße 25 Innsbruck A 6020 Austria

Department of Accelerators Nuclear Physics Institute of the CAS Rez 25068 Czech Republic

Department of Chemistry and Biochemistry Texas State University San Marcos TX 78666 USA

Department of Nuclear Chemistry Faculty of Nuclear Sciences and Physical Engineering Czech Technical University Prague Břehová 7 Prague 11519 Czech Republic

Institut de Chimie Physique UMR 8000 CNRS Université Paris Saclay Bâtiment 349 Orsay 91405 France

J Heyrovský Institute of Physical Chemistry of the CAS Dolejškova 3 Prague 182223 Czech Republic

Universität Innsbruck Institut für Ionenphysik und Angewandte Physik Technikerstraße 25 Innsbruck 6020 Austria

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