We have investigated adsorption of molecules with hydroxyl group, ROH, on sodium halide cluster ions, NanXn-1(X = F and I, n = 10-17) by mass spectrometry and by theoretical calculations. From analysis of the cluster ion intensities, the adsorption of one water molecule (R = H) is most efficient for Na13X12+ whose structure has a NaX defect from a 3 × 3 × 3 cubic structure of n = 14. This result suggests that the defect has an important role in the adsorption reaction. However, it is also found that the reactivity diminishes with increasing bulk size of the R group from H to CH3, (CH 3)2CH, and (CH3)3C. These results imply that the adsorption reactivity is dominated by steric hindrance; the smaller molecules are adsorbed inside the basket structures of Na 13X12+. Reactivity dependence on the basket size is also discussed by comparing the results of NanF n-1+ and NanIn-1+.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry