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

Abstract

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.

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Fig. 1: Schematic of the experimental setup.
Fig. 2: Experimental and simulated images for different collision energies with corresponding DCSs.
Fig. 3: Experimental and simulated images for different state preparations with corresponding DCSs.
Fig. 4: Illustration of the control over the final scattering angle for collisions into the same final state at the same collision energy by preparing different initial states.
Fig. 5: Experimental and simulated images for rotational de-excitation at low collision energies with corresponding DCSs.

Data availability

Raw scattering images, MC simulated images, extracted DCSs and theoretical DCSs are publicly available in the Zenodo data repository at https://doi.org/10.5281/zenodo.3703096.

Code availability

The quantum 2D scattering algorithm used for open-shell systems such as Ar-NO is publicly available. The MC forward-convolution program used to simulate experimental conditions is available from the author upon reasonable request.

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Acknowledgements

We thank S. Y. T. van de Meerakker for valuable discussions. This work was supported by the Army Research Office under awards W911NF-14-1-0378 and W911NF-19-1-0283 and the AFOSR under award FA9550-16-1-0018. J.K. acknowledges financial support from the US National Science Foundation, grant no. CHE-1565872 to Millard Alexander. M.B. acknowledges support from the Dutch Astrochemistry Network programme of the Netherlands Organization for Scientific Research and support from the European Research Council under the European Union’s Horizon 2020 Research and Innovation Program (grant agreement no. 817947 FICOMOL awarded to S. Y. T. van de Meerakker).

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Contributions

The project was conceived by A.G.S. The experiments were carried out by C.A., H.L. and C.P. Data analysis and simulations were performed by C.A. The RCCSD(T)-F12 potential energy surfaces were calculated by J.K. Scattering calculations employing the RCCSD(T)-F12 PESs were performed by M.B. under the guidance of G.C.G. and A.v.d.A. MRCI calculations were performed by J.Z. and C.X. under the supervision of H.G. The paper was written by C.A. and A.G.S. with contributions from all the authors.

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Correspondence to Arthur G. Suits.

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Supplementary Information

Supplementary Figs. 1–13, computational methods, supporting experimental data, data analysis and Tables 1–3.

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Amarasinghe, C., Li, H., Perera, C.A. et al. State-to-state scattering of highly vibrationally excited NO at broadly tunable energies. Nat. Chem. 12, 528–534 (2020). https://doi.org/10.1038/s41557-020-0466-8

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