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71.
Fabrikant II Caprasecca S Gallup GA Gorfinkiel JD 《The Journal of chemical physics》2012,136(18):184301
Low-energy dissociative electron attachment (DEA) to the CF(2)Cl(2) and CF(3)Cl molecules in a water cluster environment is investigated theoretically. Calculations are performed for the water trimer and water hexamer. It is shown that the DEA cross section is strongly enhanced when the attaching molecule is embedded in a water cluster, and that this cross section grows as the number of water molecules in the cluster increases. This growth is explained by a trapping effect that is due to multiple scattering by water molecules while the electron is trapped in the cluster environment. The trapping increases the resonance lifetime and the negative ion survival probability. This confirms qualitatively existing experiments on electron attachment to the CF(2)Cl(2) molecule placed on the surface of H(2)O ice. The DEA cross sections are shown to be very sensitive to the position of the attaching molecule within the cluster and the orientation of the electron beam relative to the cluster. 相似文献
72.
The cross section for bond breaking at the site of a dissociative temporary negative ion state through the dissociative electron attachment process can be considerably enhanced by the presence of a second longer-lived temporary negative ion state elsewhere in the molecule, even one quite remote from the first. In a series of chloroalkenes possessing both C-Cl and C==C bonds separated by various distances, we show that the cross sections are determined by the lifetime of the lower anion state created by the mixing of the anion states of these two moieties, with the wave function's coefficients giving the probability that the electron is located at the dissociative site. Furthermore, the lifetime of the composite anion state can be expressed in terms of these same coefficients and the lifetimes of the unmixed resonances. We also discuss how these results may give insight into the means by which strand breaks are induced in DNA by the attachment of slow electrons. 相似文献