کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
1404193 | 1501883 | 2008 | 12 صفحه PDF | دانلود رایگان |
Dimers of ketoximes are shown to represent intermediate cases of hydrogen bond-induced vibrational energy redistribution after OH stretching excitation. It is faster than in α-hydroxyester or alcohol dimers but slower than in carboxylic acid dimers. For this purpose, supersonic jet FTIR and Raman spectra of free and Ar-nanocoated acetoxime monomers, dimers and trimers are presented. By comparison to heated nozzle cyclohexanone oxime spectra, to condensed phase data and to quantum chemical calculations, a Fermi resonance description of the OH stretching dynamics in the symmetric, doubly hydrogen-bonded dimers is obtained. CN stretching and librational OH bending modes are predicted to participate in the coupling. Hydrogen bond topologies and cooperativity issues in larger oxime clusters are discussed.
Journal: Journal of Molecular Structure - Volume 880, Issues 1–3, 27 May 2008, Pages 2–13