Chemistry of aromatic cations on water clusters: Magic numbers as a mass spectroscopic diagnosis of reactivity

被引:40
作者
Courty, A [1 ]
Mons, M [1 ]
LeCalve, J [1 ]
Piuzzi, F [1 ]
Dimicoli, I [1 ]
机构
[1] CENS,CEA,SERV PHOTONS ATOMES & MOL,F-91191 GIF SUR YVETTE,FRANCE
关键词
D O I
10.1021/jp962389b
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 chemical reactivity of benzene cations in medium-sized (n similar to 25) (H2O)(n) water clusters has been investigated. After formation in a supersonic jet, the neutral Bz-(H2O)(n) species are ionized by resonance-enhanced two-photon ionization. The existence of magic numbers in the mass spectra of these cluster ions has been revealed by reflectron time-of-flight mass spectrometry. These magic numbers are assigned to size-dependent evaporation processes following the ionization. The similarities observed for the present magic numbers compared to those of protonated water clusters allow us to assign them to the formation of a protonated water cluster without ejection of the benzenoid product from the cluster ion. With this diagnosis, we present evidence for the existence of a size-dependent chemical reactivity of benzene cations: a reaction is observed in the medium size range (n similar to 20-30), whereas small clusters are known not to react. This result is compared to the chemical reactivity of toluene(+) in water clusters as well as to experimental data concerning liquid phase reactions.
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收藏
页码:1445 / 1450
页数:6
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