Comparison of the Ar(3P2) and Ar(3P) reactions with chlorine and fluorine containing molecules: Propensity for ion–core conservation

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Abstract
Optical pumping has been used to select Ar atoms in the metastable 3P2 or 3P0 state in a flowing afterglow reactor. The relative concentrations of the two metastable states were assigned from observation of the N2(C,v′) emission spectra. The isolated reactions of the Ar(3P2) and Ar(3P0) atoms with F2, NF3, Cl2, CCl4, PCl3, and SOCl2 were examined at 300 K by observation of ArCl* and ArF* formation. The total quenching rate constants for Ar(3P0) are slightly larger than for Ar(3P2). The Ar(3P2) atom reactions give only the B and C states of ArF* and ArCl*; the Ar(3P0) atom reactions give a mixture of B, C, and D states with B and D being favored. Thus, a propensity for conservation of the Ar+ ion–core configuration was found. The branching fraction for ArX* formation from Ar(3P0) with Cl2, SOCl2, F2, NF3 are similar, but those for PCl3 and CCl4 are smaller, relative to Ar(3P2). Improved rate constants for formation of individual N2(C,v′) levels from Ar(3P0) and (3P2) reacting with N2 at 300 K are given in the Appendix.

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