The Cs(7P)+H2→CsH+H reaction. II. Rotationally resolved total cross sections

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Abstract
The Cs(7P)+H2→CsH(X 1Σ+)(v‘=0,J‘)+H harpooning reaction has been studied in a crossed‐beam experiment, with electronic excitation of Cs atoms and laser‐induced fluorescence detection of CsH products performed in a coherent saturation regime. Measurements of reactive cross sections have been achieved as a function of two parameters: The collision energy Ec (0.015≤Ec≤0.15 eV) and the rotational quantum number J‘ of CsH products (0≤J‘≤16, in v‘=0). For Ec=0.09 eV, the total reactive cross sections corresponding to the two 7P fine structure levels of Cs are σ(Cs(7P1/2)+H2)=4.2×10−16 cm2 and σ(Cs(7P3/2)+H2)=10−16 cm2. These cross sections are much smaller than expected for a harpooning reaction. This is interpreted from ab initio potential energy and quantal dynamics calculations which show that the efficiency of the photochemical reaction (Cs atoms in the 7P state) is limited by the quenching processes associated with the underlying potential energy surfaces connected with Cs atoms in the 6S, 6P, 5D, and 7S states. From the present measurements, one deduces that the rate of these quenching processes is larger than 90%. The rotational distributions of products in v‘=0 measured at two collision energies (Ec=0.045 and 0.09 eV) are close to ‘‘prior’’ statistical distributions, with the same ‘‘surprisal.’’ The energy dependence of rotationally resolved cross sections (J‘ fixed, Ec variable) confirms the reaction thresholds and shows that there is no potential barrier higher than 0.015 eV on the entrance valley and the exit valley of the reactive system; it is in agreement with the dependence predicted by hemiquantal dynamical calculations performed in the frame of a harpooning model. The uncertainty on the measurement of absolute cross sections is larger than 70%, but of the order of 20% for relative cross sections.