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Additional resources for Advances in chemical physics. Vol. 142
What makes the global minimum structure of fluoroethanol particularly interesting is its chirality, although this chirality is of course not relevant for the conventional spectroscopy of the monomer. Due to the intramolecular OÀ ÀH Á Á ÁF contact, hydrogen-bonded 2-fluoroethanol dimers may be expected to be structurally less diverse than ethanol dimers. Indeed, there is no indication for dimers built from metastable monomer conformations in the supersonic jet expansion . However, the fluorine atom of the hydrogen bond donor alcohol can be engaged in a secondary interaction with the OÀ ÀH group of the acceptor, which would be ‘‘dangling’’ in the case of regular ethanol dimers.
Chirality recognition is only weak, but the experimental evidence indicates that the heteroconfigurational dimer may be slightly more stable, opposite to the case of ethanol. We note that 2,2-difluoroethanol behaves quite similar to fluoroethanol. Again, there is only one dominant monomer conformation and up to four dimer isomers are observed. However, in this case the relaxation behavior is completely opposite. The least red-shifted isomers are now most stable and correlate well with associated complexes.
IR and Raman OH stretching spectra of n-propanol monomers and dimers reflecting conformational diversity. The Raman spectrum reveals the dominance of the internally hydrogenbonded Gt monomer most clearly, whereas the IR spectrum indicates more than five different dimer conformations in the red-shifted dimer spectrum . is much inferior . For a spectral separation of the different conformations, Raman spectroscopy proves to be powerful, because the spectra are dominated by narrow Q-branches.