By Rice S. (ed.)
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Extra resources for Advances in Chemical Physics,
Out of the nine distinguishable dimer conformers in a simple counting scheme involving acceptor lone pairs , about six may be expected to be relatively stable  Earlier theoretical studies were not very conclusive concerning the subtle energy sequence of these isomers. For an accurate theoretical description of dimers, it is essential that the differences in monomer conformation are well-described. Direct absorption measurements in He supersonic jet expansions [65, 157] and Raman jet spectroscopy  reveal at least three, more likely four, competing dimer conformers even at low temperatures.
The recently proposed size-specific VUV-IR technique is not practical for this purpose, because it produces strongly broadened, spectrally shifted and most likely fragmentation-affected bands for methanol trimer and larger clusters . The anharmonicity of the OÀ ÀH stretching oscillators changes with cluster size. For the monomer, the anharmonicity constant is on the order of 90 cm 1 . A coarse deuteration analysis [16, 88] suggests that it increases by more than 20% upon trimer and tetramer formation .
Crossed Beam Techniques Cluster size assignment is often a challenge for direct absorption or light scattering techniques that do not provide reliable mass information. For dimers, a combination of pressure or concentration dependence and spectral survey is usually unambiguous. In favorable cases, this also applies to trimers, tetramers, and maybe pentamers. Beyond that size, some kind of mass information is required. Aliphatic alcohols and their clusters suffer from heavy fragmentation upon ionization.