The dynamics and kinematics of the electron transfer reactions of CF32+ with Ar
Publication Type:Journal Article
Source:Molecular Physics: An International Journal at the Interface Between Chemistry and Physics, Taylor & Francis Group, Volume 103, Issue 13, p.1809-1819 (0)
The electron transfer reactions between CF TMPH1809math002 and Ar have been studied using a position-sensitive coincidence time-of-flight mass spectrometer. The spectra show the formation of CF TMPH1809math003, CF TMPH1809math004 and CF TMPH1809math005 ions, accompanied by Ar+ ions, by dissociative and non-dissociative electron transfer reactions. Analysis of the PSCO data shows that the CF TMPH1809math006 and CF TMPH1809math007 ions are formed by reactions of ground state CF TMPH1809math008(2B2) ions. The CF TMPH1809math009 product is formed in high lying vibrational states of its ground electronic state, just below the dissociation asymptote to TMPH1809math010. The formation of CF TMPH1809math011 proceeds via a sequential mechanism, involving the population of highly excited vibrational levels of the ground electronic state of CF TMPH1809math012 which dissociate to CF TMPH1809math013(2A1) + F when the CF TMPH1809math014 is well separated from the Ar+ ion. No evidence of complexation is observed. The energy dependence of the experimental yield of the CF+ ion is consistent with it arising from a reaction of an electronic excited state of CF TMPH1809math015, as proposed in a previous study of this collision system. The unimolecular dissociation of the reactant dications is also observed and indicates that these ions are predominantly in their ground (2B2) electronic state. The kinetic energy release of this unimolecular reaction indicates the metastable well of the CF TMPH1809math016(2B2) state is approximately 3 eV deep and also shows that CF TMPH1809math017(2B2) ions well below the barrier to charge separation can dissociate on the time-scale of the experiment. This observation implicates predissociation, possibly via a repulsive dication state, as the mechanism for the unimolecular charge separation of the ground state of CF TMPH1809math018.