Cold collisions of hot molecules

In this Perspective, we review our recent work on rotationally inelastic collisions of highly vibrationally excited NO molecules prepared in single rotational and parity levels at v = 10 using stimulated emission pumping (SEP). This state preparation is employed in a recently developed crossed molecular beam apparatus where two nearly copropagating molecular beams achieve an intersection angle of 4° at the interaction region. This near-copropagating beam geometry of the molecular beams permits very wide tuning of the collision energy, from far above room temperature down to 2 K where we test the theoretical treatment of the attractive part of the potentials and the difference potential for the first time. We have obtained differential cross sections for state-to-state collisions of NO (v = 10) with Ar and Ne in both spin-orbit manifolds using velocity map imaging. Overall good agreement of the experimental results was seen with quantum mechanical close-coupling calculations done on both coupled-cluster and multi-reference configuration interaction potential energy surfaces. Probing cold collisions of NO carrying ∼2 eV of vibrational excitation allows us to test state-of-the-art theory in this extreme nonequilibrium regime.