Observation of Rainbows in the Rotationally Inelastic Scattering of NO with CH₄

Using a combination of velocity-map imaging and resonance-enhanced multiphoton ionization detection with crossed molecular beam scattering, the dynamics of rotational energy transfer have been examined for NO in collisions with CH₄ at a mean collision energy of 700 cm. The images of NO scattered into individual rotational (j_NO^') and spin-orbit (Ω) levels typically exhibit a single broad maximum that gradually shifts from the forward to the backward scattering direction with increasing rotational excitation (i.e., larger Δj_NO). The rotational rainbow angles calculated with a two-dimensional hard ellipse model show reasonable agreement with the observed angles corresponding to the maxima in the differential cross sections extracted from the images for higher Δj_NO transitions, but there are clear discrepancies for lower Δj_NO (in particular, final rotational levels with j_NO^' = 7.5 and 8.5). The sharply forward scattered angular distributions for these lower Δj_NO transitions better agree with the predictions of an L-type rainbow model. The more highly rotationally excited NO appears to coincide with low rotational excitation of the co-product CH₄, indicating a degree of rotational product-pair anticorrelation in this bimolecular scattering.