By Rice S. (ed.)
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Extra resources for Advances in Chemical Physics,
Hydrogen bond dynamics in alcohol clusters E. 19 UV–IR Coupling Once the alcohol or at least the cluster contains a soft ionization or fluorescence chromophore, a wide range of experimental tools opens up. Experimental methods for hydrogen-bonded aromatic clusters have been reviewed before [3, 19, 175]. Fluorescence can sometimes behave erratically with cluster size , and short lifetimes may require ultrafast detection techniques . However, the techniques are very powerful and versatile in the study of alcohol clusters.
Harmonic predictions of this red shift are much larger, even at fairly high levels of electronic structure treatment . This may be due to higher-order electron correlation and anharmonic effects . Upon deuteration of the bridging proton, the shift reduces to 80 cm 1 , again much less than the best harmonic predictions. Even deuteration of the free OÀ ÀH group affects the red shift of the hydrogen-bonded OÀ ÀH noticeably, although the two oscillators are welldecoupled . This confirms the high sensitivity of vibrational frequency shifts to details of the hydrogen bond environment.
As an example, the overtone-deduced anharmonicity of methanol monomer in a nitrogen matrix  is 85 cm 1 , whereas in vacuum  it is 92 cm 1 . The deuteration-estimated anharmonicity is 91 cm 1 for the monomer and 97 cm 1 for the dimer donor in the nitrogen matrix, whereas it is 87 cm 1 for the monomer and 89 cm 1 for the dimer donor in vacuum. Clearly, only a vacuum overtone measurement would be fully conclusive, but as the matrix study  26 martin a. suhm shows, this is very challenging for methanol dimer and completely out of reach for trimers.
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