| Abstract
| - Weakly bound 1:1 complexes formed between CS2 and a dihalogen molecule XY = Cl2, Br2, BrCl, ICl, orIBr have each been trapped in an Ar matrix and hence investigated experimentally by their IR spectra as wellas theoretically by MP2 and density functional calculations. A planar structure, with an intermolecular angleclose to 90°, is expected for such a SCS···XY molecular complex. Moreover, for each system involvinga heteronuclear dihalogen, two possible complexes exist, viz., SCS···XY and SCS···YX. The calculatedstructures, vibrational properties, and binding energetics of the complexes are analyzed, and the NBO formalismis used to interpret their bonding properties. The IR spectra of the complexes thus simulated provided vitalguidance for the interpretation of the matrix spectra. For example, complexation was predicted and observed(i) to induce red shifts of the principal absorptions associated with both the CS2 and XY components and (ii)to result, through the change in symmetry, in activation of some modes that are IR-silent for the freecomponents.
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