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• W2059361903 endingPage "516" @default.
• W2059361903 startingPage "507" @default.
• W2059361903 abstract "Reactivity of the dication CO22+ in dependence on its internal energy was studied in collision with CO2 and CO. The dication was obtained by photoionization of the CO2 molecule by synchrotron radiation and the guided beam apparatus CERISES was used in these studies. Spontaneous dissociation of CO22+ to CO+ and O+ was observed without any target gas in the reaction cell. With CO2 or CO as a target gas, CO+ and O+ fragment ions were formed as products of dissociative charge transfer, while the contribution of collision-induced dissociation of the reactant CO22+ to their formation was found negligible. The CO+ yield showed a considerable dependence on the internal energy of the reactant dication CO22+: the branching ratio CO+/O+ increased gradually with photon energy between 38.7 and 39.4 eV. We interpret this observation as being due to the increase in the instantaneous distances at the extrema of vibrational motion of the dication with increasing internal energy. This modifies the Franck-Condon factors in the charge transfer process and leads to a preferential population of the vibrationally excited states of the product cation CO2+(C) known to lead exclusively to the dissociation products CO++O. An indirect mechanism that requires the coupling of the first excited (a) state of the dication with the higher vibrational states of the CO22+ (X) state is proposed to explain the threshold behaviour observed in our results." @default.
• W2059361903 created "2016-06-24" @default.
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• W2059361903 date "2003-08-01" @default.
• W2059361903 modified "2023-10-11" @default.
• W2059361903 title "Internal energy effects in the reactivity of CO22+ doubly charged molecular ions with CO2 and CO" @default.
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• W2059361903 doi "https://doi.org/10.1016/s1387-3806(03)00157-x" @default.
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