Experimental and computational study of neutral xenon halides (XeX) in the gas phase for X=F, Cl, Br, and I

Detlef Schröder, Jeremy N. Harvey, Massimiliano Aschi, and Helmut Schwarz
Institut für Organische Chemie, Strasse des 17. Juni 135, D-10623 Berlin, Germany

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We report a combined experimental and theoretical study of the xenon monohalide radicals XeX (X=F, Cl, Br, and I) together with their cationic and anionic counterparts XeX + and XeX - . In brief, the XeX + cations are characterized by reasonably strong chemical bonds with significant charge-transfer stabilization, except for X=F. In contrast, the neutral XeX radicals as well as the XeX - 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 XeX and XeX - 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 XeX - 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 XeX + XeXXeX - can be achieved allowing one to generate neutral XeX radicals withhttp:/ lifetimes of at least a few microseconds for X=F and I.