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• W2059263195 abstract "Chemiluminescent reactions of hyperthermal Ca(3P) with CF2Cl2 and CF2CCl2 were studied in a beam-gas arrangement under single collision conditions. Emissions associated with the A(2ΠΩ) → X(2Σ+) and the B(2Σ+) → X(2Σ+) transitions from CaCl and CaF were observed for both reactions. The chemical and electronic branching ratios were determined for these reactions, and different results were obtained for each one. The different behavior was rationalized by a simple MO pictures. For the case of the reaction with CF2Cl2 it was assumed that an electron from Ca(3P) is transferred to a σ*(C−Cl) orbital in CF2Cl2 which, at higher translational energies can also enter into a σ*(C−F) orbital of the same molecule. In both cases the molecular anion produced is short-lived and will undergo fast decay to Cl- or F- to yield CaCl and CaF. For the reaction with CF2CCl2 the electron from Ca(3P) is transferred to a π* orbital of the reagent molecule that generates a relatively stable molecular anion with 2Π symmetry. This anion subsequently cross over several repulsive 2Σ surfaces associated with σ* orbitals of the C−Cl and the C−F bonds, to dissociate into Cl- or F- to produce CaCl and CaF. The electronic branching ratios are in good agreement with statistical distribution based on information theory approach, assuming the rigid rotor harmonic oscillator (RROH) approximation for the reaction with CF2Cl2 and the formation of a collision complex for the reaction with CF2CCl2." @default.
• W2059263195 created "2016-06-24" @default.
• W2059263195 creator A5026880247 @default.
• W2059263195 creator A5071808658 @default.
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• W2059263195 date "2003-08-12" @default.
• W2059263195 modified "2023-10-03" @default.
• W2059263195 title "Chemical and Electronic Branching Ratios in the Chemiluminescent Reactions of Hyperthermal Ca(³P) Atoms with CF₂Cl₂ and CF₂CCl₂" @default.
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• W2059263195 doi "https://doi.org/10.1021/jp026928q" @default.
• W2059263195 hasPublicationYear "2003" @default.
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