This paper was published as Journal of Physical Chemistry A, 2007, 111 (34), pp. 8344–8351. Copyright © 2007 American Chemical Society. It is available from http://pubs.acs.org/doi/abs/10.1021/jp073637e. Doi: 10.1021/jp073637eMetadata only entryThe first mass-selective vibrational spectra have been recorded for Na(NH3)n clusters. Infrared spectra have been obtained for n = 3−8 in the N−H stretching region. The spectroscopic work has been supported by ab initio calculations carried out at both the DFT(B3LYP) and MP2 levels, using a 6-311++G(d,p) basis set. The calculations reveal that the lowest energy isomer for n ≤ 6 consists of a single solvation shell for the NH3 molecules, although in the case of n = 5 and 6 there are two-shell isomers that are reasonably close in energy to the single-shell global potential energy minimum. The infrared spectra concur with the ab initio predictions, showing similar spectra for the n = 3−6 clusters but a marked change for n = 7 and 8. The change in spectroscopic features for n ≥ 7 is indicative of molecules entering a second solvation shell, i.e., the inner solvation shell around the sodium atom can accommodate a maximum of six NH3 molecules
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