Advances in Chemical Physics, by Rice S. (ed.)

By Rice S. (ed.)

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Matrix isolation studies are also available [262, 273]. We are currently investigating the jet spectra of 2,2,2-trichloroethanol and its clusters. In contrast to trifluoroethanol, more than one dimer conformation is found, thus underscoring the singularity of the previously described chirality synchronization phenomenon. Some chloropropanols are permanently chiral variants of 2-chloroethanol and therefore show a preference between the two gauche conformations that are stabilized by an intramolecular hydrogen bond.

Librational infrared spectra of methanol clusters [93] (bands B and C due to the tetramer, broad profile due to large clusters, cluster size increases from bottom to top) compared to the absorptions in amorphous and crystalline (zig zag) solid methanol [40]. The large clusters compare well to the amorphous solid, whereas the ring tetramer may be viewed as a small model of the zig zag chains in the crystal. Note that the high frequency band C acquires IR intensity through puckering of the methyl groups above (u) and below (d) the hydrogen bond plane.

Therefore, an interesting class of model compounds is represented by hydroxyesters. Glycolates are the simplest representatives. They form clusters ÀO hydrogen in which OÀ ÀH Á Á ÁOÀ ÀH hydrogen bonds compete with OÀ ÀH Á Á ÁCÀ bonds. The latter are intrinsically stronger, but the former offer cooperative enhancement, if more than two OÀ ÀH groups are involved [274]. When a methyl group is added to the OÀ ÀH-carrying carbon, a chiral center is created in the immediate neighborhood of the OÀ ÀH group.

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