Gas phase infrared multiple-photon dissociation spectra of methanol, ethanol and propanol proton-bound dimers, protonated propanol and the propanol/water proton-bound dimer

被引:79
作者
Fridgen, TD [1 ]
MacAleese, L
McMahon, TB
Lemaire, J
Maitre, P
机构
[1] Mem Univ Newfoundland, Dept Chem, St John, NF A1B 3X7, Canada
[2] Univ Paris 11, CNRS, UMR 8000, Chim Phys Lab, F-91405 Orsay, France
[3] Univ Waterloo, Dept Chem, Waterloo, ON N2L 3G1, Canada
关键词
D O I
10.1039/b516661f
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The infrared multiphoton dissociation (IRMPD) spectra of three homogenous proton-bound dimers are presented and the major features are assigned based on comparisons with the neutral alcohol and with density functional theory calculations. As well, the IRMPD spectra of protonated propanol and the propanol/water proton-bound dimer (or singly hydrated protonated propanol) are presented and analysed. Two primary IRMPD photoproducts were observed for each of the alcohol proton bound dimers and were found to vary with the frequency of the radiation impinging upon the ions. For example, when the proton-bound dimer absorbs weakly a larger amount of S(N)2 product, protonated ether and water, are observed. When the proton-bound dimer absorbs more strongly, an increase in the simple dissociation product, protonated alcohol and neutral alcohol, is observed. With the aid of RRKM calculations this frequency dependence of the branching ratio is explained by assuming that photon absorption is faster than dissociation for these species and that only a few photons extra are necessary to make the higher-energy dissociation channel (simple cleavage) competitive with the lower energy (S(N)2) reaction channel.
引用
收藏
页码:955 / 966
页数:12
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