Quantum reactive scattering calculations for the cold and ultracold Li + LiNa → Li2 + Na reaction
Brian K. Kendrick
A first-principles based quantum dynamics study of the Li + LiNa(v = 0, j = 0) → Li2(v′, j′) + Na reaction is reported for collision energies spanning the ultracold (1 nK) to cold (1 K) regimes. A full-dimensional ab initio potential energy surface for the ground electronic state of Li2Na is utilized that includes an accurate treatment of the long-range interactions. The Li + LiNa reaction is barrierless and exoergic and exhibits a deep attractive potential well that supports complex formation. Thus, significant reactivity occurs even for collision temperatures approaching absolute zero. The reactive scattering calculations are based on a numerically exact time-independent quantum dynamics methodology in hyperspherical coordinates. Total and rotationally resolved rate coefficients are reported at 56 collision energies and include all contributing partial waves. Several shape resonances are observed in many of the rotationally resolved rate coefficients and a small resonance feature is also reported in the total rate coefficient near 50 mK. Of particular interest, the angular distributions or differential cross sections are reported as a function of both the collision energy and scattering angle. Unique quantum fingerprints (bumps, channels, and ripples) are observed in the angular distributions for each product rotational state due to quantum interference and shape resonance contributions. The Li + LiNa reaction is under active experimental investigation so that these intriguing features could be verified experimentally when sufficient product state resolution becomes feasible for collision energies below 1 K.
The Journal of Chemical Physics•Mar 22, 2021•15 citations