Experimental and theoretical total state-selected and state-to-state absolute cross sections. I. The H+2(X,v′)+Ar reaction

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Abstract
Total state‐selected and state‐to‐state absolute cross sections for the reactions, H+2(X̃,v’=0–4)+Ar→H2(X,v) +Ar+(2P3/2,1/2) [reaction (I)], ArH++H [reaction (II)], and H++H+Ar [reaction (III)], have been measured in the center‐of‐mass collision energy (Ec.m.) range of 0.48–100 eV. Experimental state‐selected cross sections for reactions (I) and (II) measured at Ec.m.=0.48–0.95 eV are in agreement with those reported previously by Tanaka, Kato, and Koyano [J. Chem. Phys. 7 5, 4941 (1981)]. The experiment shows that prominent features of the cross sections for reactions (I) and (II) are governed by the close resonance of the H+2(X̃,v’=2)+Ar and H2(X,v=0)+Ar+(2P1/2) vibronic states. At Ec.m.≤3 eV, the vibrational state‐selected cross section for the charge transfer reaction (I) is peaked at v’=2. The enhancement of the charge transfer cross section for v’=2 as compared to other v’ states of reactant H+2 increases as Ec.m. is decreased. The state‐to‐state cross sections for reaction (I),measured at Ec.m.≤3 eV, show that the enhancement for the charge transfer cross section for v’=2 is due to the preferential population of Ar+(2P1/2). At Ec.m.=0.48–0.95 eV and v’=2, nearly 80% of the charge transfer product Ar+ ions are formed in the 2P1/2 state. However, at Ec.m.>5 eV, the intensity for charge transfer product Ar+(2P3/2) is greater than that for Ar+(2P1/2). Contrary to the strong vibrational dependence of the cross section for reaction (I), the cross section for reaction (II) is only weakly dependent on the vibrational state of H+2. At Ec.m.≤3 eV, the cross section for the formation of ArH+ is the lowest for v’=2 compared to other v’ states, an observation attributed to the competition of the nearly resonant Ar+(2P1/2)+H2(X,v=0) charge transfer channel. The cross section for reaction (II) decreases with increasing Ec.m.. At Ec.m.≥20 eV, the cross sections for the formation of ArH+ become negligible compared to those for Ar+. The appearance energies for the collision‐induced dissociation H+2(X̃,v’=0–4) are consistent with the thermochemical threshold for reaction (III). The cross sections the formation of H+ are ≤20% of those for H+2. Theoretical state‐to‐state cross sections for reaction (I) at Ec.m.=19.3 and 47.6 eV calculated using the nonreactive infinite‐order sudden approximation are found to be in fair agreement with experimental results.

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