Rice S. (ed.)'s Advances in Chemical Physics, PDF

By Rice S. (ed.)

ISBN-10: 0470464992

ISBN-13: 9780470464991

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The UV chromophore can be exploited for sensitive detection of the IR spectrum [35, 36, 120, 179]. Time-domain experiments become possible [21], which show that the initial energy flow out of the OÀ ÀH stretching mode occurs primarily via CÀ ÀH stretching and bending doorway states. Like in the case of carboxylic acid dimers [245], the role of the hydrogen bond is to shift the OÀ ÀH stretching mode closer to these doorway states and thus to accelerate the initial energy flow. In terms of binding energy, classical hydrogen bonding may be enhanced by the increased acidity of the phenolic OÀ ÀH, if the acceptor alcohol is nonphenolic [149, 182].

While the monomer vibrational dynamics is in general well-studied [214 217], different values for the fundamental OÀ ÀH stretching band center are in use [63, 64, 75, 173, 189, 218]. Based on combined Raman and IR evidence, a value of 3684 3686 cm 1 appears well-justified [16, 65, 77, 82, 216]. It serves as an important reference for vibrational red shifts in methanol clusters. The methanol dimer is structurally well-characterized [143]. It features a clear distinction between hydrogen bond donor and acceptor OÀ ÀH groups.

The prototype for molecules involving three alcohol groups is glycerol. Its hydrogen bond topology [280, 281] is strongly temperature-dependent, and conformer relaxation in the jet expansion [282] appears to be efficient. In order to model sugars more closely, further functionalities have to be included. Glycidol may be considered as a simplified model that includes an O-heterocycle. Its dimer has been studied successfully with respect to chirality recognition phenomena [111]. More realistic models for open sugars involve keto or aldehyde groups.

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


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