科研之友
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摘要
By tuning the alkyl substituent of a carboxylic acid, the intermolecular modes in its hydrogen-bonded dimer can be reordered. These modes are detected at low vibrational congestion for formic, acetic, propiolic and pivalic acid using Raman jet spectroscopy. By probing the shock zone between the free jet and the background gas, a continuous evolution of the dimer spectra between cryogenic and ambient temperatures is achieved. Analysis of the dimer stretching mode within a pseudo-diatomic model quantifies substitution effects on the hydrogen-bond force constant. They do not correlate with effects on predicted overall dimer binding energies. The evolution of the spectra with increasing cluster size reveals the stacking structure of supra-dimeric aggregates.
- 出版日期2010
