Advances in Chemical Physics, - download pdf or read online

By Rice S. (ed.)

ISBN-10: 0470464992

ISBN-13: 9780470464991

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C. Raman Scattering Whenever symmetry or quasi-symmetry plays a role, particularly in cyclic alcohol clusters, spontaneous Raman scattering off supersonic jet expansions provides valuable complementary information on the cluster dynamics [16, 77]. Even for nonsymmetric clusters and monomer conformations, it may be used to complement IR spectroscopy, because the Raman rovibrational selection rules often ensure a more narrow band profile [69, 161]. The applicability of spontaneous Raman scattering to jet-generated hydrogen-bonded clusters is a very recent advance [77], whereas it is more established for the characterization of jet expansions in general [162] and complexes of simple molecules [163, 164].

In contrast to earlier evidence around room temperature [37], the low-temperature environment appears to be able to stabilize aggregates beyond the dimer [65]. Crystal structure determination even reveals tetrahedral arrangements of the OÀ ÀH groups in extremely bulky alcohol tetramers, although the proton positions are disordered [239]. The hydrogen-bond-induced red shift in branched alcohol dimers can be predicted using a fairly simple molecular modeling approach, as long as conformational isomerism does not complicate the picture [72].

Interconversion between the two nearly isoenergetic, but topologically different, isomers involves a barrier of close to 10 kJ/mol (see Fig. 9). Therefore, it is not easy to explain the complete Figure 9. The torsional potential of trifluoroethanol (dashed line, gþ/t/g , in analogy to the ethanol case shown in Fig. 4) is only distorted slightly if it acts as a hydrogen bond acceptor toward a gþ trifluoroethanol unit [30] (full line). Nevertheless, only the compact inserted homochiral dimer (left, ijcjhom) is observed in the jet experiment, not the compact associated heterochiral dimer (right, ajcjhet).

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


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