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Microwave Spectrum, Structure, and Hyperfine Constants of Kr–AgCl: Formation of a Weak Kr–Ag Covalent Bond

✍ Scribed by Linda M Reynard; Corey J Evans; Michael C.L Gerry


Publisher
Elsevier Science
Year
2001
Tongue
English
Weight
155 KB
Volume
206
Category
Article
ISSN
0022-2852

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✦ Synopsis


The pure rotational spectrum of the complex Kr-AgCl has been measured between 8-15 GHz using a cavity pulsed-jet Fourier transform microwave spectrometer. The complex was found to be linear and relatively rigid, with a Kr-Ag bond length of ∼2.641 Å. The Kr-Ag stretching frequency was estimated to be 117 cm -1 . Ab initio calculations performed at the MP2 level of theory gave the geometry, vibration frequencies, Kr-Ag bond dissociation energy, and orbital populations. The Kr-Ag bond dissociation energy was estimated to be ∼28 kJ mol -1 . The Kr-Ag force constant and dissociation energy are greater than those of Ar-Ag in Ar-AgCl. The chlorine nuclear quadrupole coupling constants show slight changes on complex formation. Ab initio orbital population analysis shows a small shift in σ -electron density from Kr to Ag on complex formation. The combined experimental and ab initio results are consistent with the presence of a weak Kr-Ag covalent bond.