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.

Differential Cross Sections for Cold, State-to-State Spin-Orbit Changing Collisions of NO(v = 10) with Neon.

Inelastic scattering processes have proven a powerful means of investigating molecular interactions, and much current effort is focused on the cold and ultracold regime where quantum phenomena are clearly manifested. Studies of collisions of the open shell nitric oxide (NO) molecule have been central in this effort since the pioneering work of Houston and co-workers in the early 1990s. State-to-state scattering of vibrationally excited molecules in the cold regime introduces challenges that test the suitability of current theoretical methods for ab initio determination of intermolecular potentials, and concomitant electronically nonadiabatic processes raise the bar further. Here we report measurements of differential cross sections for state-to-state spin-orbit changing collisions of NO (v = 10, Ω″ = 1.5, and j″ = 1.5) with neon from 2.3 to 3.5 cm-1 collision energy using our recently developed near-copropagating beam technique. The experimental results are compared with those obtained from quantum scattering calculations on a high-level set of coupled cluster potential energy surfaces and are shown to be in good agreement. The theoretical results suggest that distinct backscattering in the 2.3 cm-1 case arises from overlapping resonances.

A versatile molecular beam apparatus for cold/ultracold collisions.

We have developed an apparatus capable of performing intrabeam and near-copropagating beam scattering experiments at collision energies from room temperature to below 1 K where interesting quantum phenomena can be observed. A detailed description of the major components of the apparatus, single and dual molecular beam valves, high speed chopper, and the discharge source, is presented. With the intrabeam scattering setup, a novel dual-slit chopper permits collision energies down to millikelvins with a collision energy spread of 20%. With the near-copropagating beam configuration, state-to-state differential cross sections for rotationally inelastic collisions of highly vibrationally excited NO molecules with Ar have been measured at broadly tunable energies documenting the versatility of the instrument. Future applications in stereodynamics and cold state-to-state collisions of vibrationally excited polyatomic molecules are briefly discussed.

State-to-state scattering of highly vibrationally excited NO at broadly tunable energies.

Experimental developments continue to challenge the theoretical description of molecular interactions. One key arena in which these advances have taken place is in rotationally inelastic scattering. Electric fields have been used with great success to select the initial quantum state and slow molecules for scattering studies, revealing novel stereodynamics, diffraction oscillations and scattering resonances. These have enjoyed excellent agreement with quantum scattering calculations performed on state-of-the-art coupled-cluster potential energy surfaces. To date these studies have largely employed reactants in the ground vibrational state (v = 0) and the lowest low-field-seeking quantum state. Here we describe the use of stimulated emission pumping to prepare NO molecules in arbitrary single rotational and parity states of v = 10 for inelastic scattering studies. These are employed in a near-copropagating molecular beam geometry that permits the collision energy to be tuned from above room temperature to 1 K or below, with product differential cross-sections obtained by velocity map imaging. This extremely nonequilibrium condition, not found in nature, tests current theoretical methods in a new regime.

Differential Cross Sections for State-to-State Collisions of NO( v = 10) in Near-Copropagating Beams.

State-to-state differential cross sections for rotationally inelastic collisions of vibrationally excited NO with Ar have been measured in a near-copropagating crossed beam experiment at collision energies of 530 and 30 cm-1. Stimulated emission pumping (SEP) to prepare NO in specific rovibrational levels is coupled with direct-current slice velocity map imaging to obtain a direct measurement of the differential cross sections. The use of nearly copropagating beams to achieve low NO-Ar collision energies and broad collision energy tuning capability are also demonstrated. The experimental differential cross sections (DCSs) for NO in v = 10 in specific rotational and parity states are compared with the corresponding DCSs predicted for NO in v = 0 obtained from quantum mechanical close coupling calculations to highlight the differences between the NO( v = 10)-Ar and NO( v = 0)-Ar interaction potentials.