Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 127, Issue 14, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.2776334
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Spectra of clusters formed between lithium atoms and methylamine molecules are reported for the first time. Mass-selective infrared spectra of Li(NH2CH3)(n) have been recorded in both the N-H and C-H stretching fundamental regions. The infrared spectra are broadly in agreement with ab initio predictions, showing redshifted N-H stretching bands relative to free methylamine and a strong enhancement of the N-H stretching fundamentals relative to the C-H stretching fundamentals. The ab initio calculations suggest that, for n=3, the methylamine molecules bunch together on one side of the lithium atom to minimize repulsive interactions with the unpaired electron density. The addition of a fourth methylamine molecule results in closure of the inner solvation shell and, thus, Li(NH2CH3)(5) is forced to adopt a two-shell coordination structure. This is consistent with neutron diffraction studies of concentrated lithium/methylamine solutions, which also suggest that the first solvation shell around the lithium atom can contain a maximum of four methylamine molecules. (C) 2007 American Institute of Physics.
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