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Physical Chemistry Chemical Physics

High quality research in physical chemistry, chemical physics and biophysical chemistry.




Paper

Phys. Chem. Chem. Phys., 2004, 6, 3248 - 3256, DOI: 10.1039/b404953p


Insights into the xenon–silver halide interaction from a rotational spectroscopic study of XeAgF and XeAgCl

Stephen A. Cooke and Michael C. L. Gerry


XeAgF and XeAgCl have been prepared by laser ablation of Ag metal in the presence of xenon and SF6 or xenon and Cl2, respectively. Rotational spectra for 12 isotopomers of XeAgF and 16 isotopomers of XeAgCl have been recorded. Analysis of the spectra indicates that (i) both chemical systems are unusually strongly bound compared to conventional van der Waals complexes, (ii) significant charge rearrangement occurs at the xenon nucleus upon formation of both XeAgF and XeAgCl as shown by the 131Xe nuclear quadrupole coupling constants and (iii) in both XeAgF and XeAgCl the Xe–Ag distance is small compared to the sum of the Xe van der Waals radius and the Ag+ ionic radius. An ab initio study of the two species has been performed. The combined experimental and theoretical investigations indicate that the Xe–Ag interaction is not easily described, but that there is some evidence for weak chemical bonding.