We report a combined experimental and theoretical study of the xenon monohalide radicals (X=F, Cl, Br, and I) together with their cationic and anionic counterparts and In brief, the cations are characterized by reasonably strong chemical bonds with significant charge-transfer stabilization, except for X=F. In contrast, the neutral radicals as well as the anions can mostly be described in terms of van der Waals complexes and exhibit bond strengths of only a few tenths of an electron volt. For both and the fluorides (X=F) are the most strongly bound among the xenon halides due to significant covalency in the neutral radical, and to the large charge density on fluoride in the anion, respectively. Mass spectrometric experiments reveal the different behavior of xenon fluoride as compared to the other halides, and in kiloelectron-volt collisions sequential electron transfer according to can be achieved allowing one to generate neutral radicals with lifetimes of at least a few microseconds for X=F and I.
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