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Physical Chemistry Chemical Physics

Non-adiabatic quantum interference in the ultracold Li + LiNa → Li 2 + Na reaction

Brian K. Kendrick, Hui Li, Ming Li, Svetlana Kotochigova, James F. E. Croft, N. Balakrishnan

Published Jan 1, 2021• 48 citations
Publisher

Abstract

Electronically non-adiabatic effects play an important role in many chemical reactions. However, how these effects manifest in cold and ultracold chemistry remains largely unexplored. Here for the first time we present from first principles the non-adiabatic quantum dynamics of the reactive scattering between ultracold alkali-metal LiNa molecules and Li atoms. We show that non-adiabatic dynamics induces quantum interference effects that dramatically alter the ultracold rotationally resolved reaction rate coefficients. The interference effect arises from the conical intersection between the ground and an excited electronic state that is energetically accessible even for ultracold collisions. These unique interference effects might be exploited for quantum control applications such as a quantum molecular switch. The non-adiabatic dynamics are based on full-dimensional ab initio potential energy surfaces for the two electronic states that includes the non-adiabatic couplings and an accurate treatment of the long-range interactions. A statistical analysis of rotational populations of the Li2 product reveals a Poisson distribution implying the underlying classical dynamics are chaotic. The Poisson distribution is robust and amenable to experimental verification and appears to be a universal property of ultracold reactions involving alkali metal dimers.

DOI
10.1039/d0cp05499b

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Electronically non-adiabatic effects play an important role in many chemical reactions. However, how these effects manifest in cold and ultracold chemistry remains largely unexplored. Here for the first time we present from first principles the non-adiabatic quantum dynamics of the reactive scattering between ultracold alkali-metal LiNa molecules and Li atoms. We show that non-adiabatic dynamics induces quantum interference effects that dramatically alter the ultracold rotationally resolved reaction rate coefficients. The interference effect arises from the conical intersection between the ground and an excited electronic state that is energetically accessible even for ultracold collisions. These unique interference effects might be exploited for quantum control applications such as a quantum molecular switch. The non-adiabatic dynamics are based on full-dimensional ab initio potential energy surfaces for the two electronic states that includes the non-adiabatic couplings and an accurate treatment of the long-range interactions. A statistical analysis of rotational populations of the Li2 product reveals a Poisson distribution implying the underlying classical dynamics are chaotic. The Poisson distribution is robust and amenable to experimental verification and appears to be a universal property of ultracold reactions involving alkali metal dimers.
Non-adiabatic quantum interference effects and chaoticity in the ultracold Li + LiNa →\to→ Li2_22​ + Na reaction
Electronically non-adiabatic effects play an important role in many chemical reactions. How these effects manifest in cold and ultracold chemistry remain largely unexplored. Here, through first principles non-adiabatic quantum dynamics calculations of the Li + LiNa →\to→ Li2_22​ + Na chemical reaction, it is shown that non-adiabatic dynamics induces quantum interference effects that dramatically alter the ultracold rotationally resolved reaction rate coefficients. The interference effect arises from a conical intersection between the ground and an excited electronic state that is energetically accessible even for ultracold collisions. These unique interference effects might be exploited for quantum control applications as a quantum molecular switch. A statistical analysis of rotational populations of the Li2_22​ product reveals a Poisson distribution implying an underlying classically chaotic dynamics. The Poisson distribution is robust and amenable to experimental verification and appears to be a universal property of ultracold reactions involving alkali metal dimers.
Synopsis We report non-adiabatic dynamics of the Li+LiNa→Li2+Na chemical reaction at cold and ultracold temperatures employing accurate ab initio electronic potential energy surfaces in a quantum dynamics formulation employing a diabatic representation. Results are compared against those from a single adiabatic ground state potential energy surface and a universal model based on the long-range interaction potential. We discuss signatures of non-universal behavior in the total rate coefficients as well as strong non-adiabatic effects in the state-to-state rotationally resolved rate coefficients.
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.
Ultracold chemical reactions of weakly bound triplet-state alkali metal dimer molecules have recently attracted much experimental interest. We perform rigorous quantum scattering calculations with a new ab initio potential energy surface to explore the chemical reaction of spin-polarized NaLi( a 3 Σ + ) and Li( 2 S) to form Li 2 ( a 3 Σ u + ) and Na( 2 S). The reaction is exothermic and proceeds readily at ultralow temperatures. Significantly, we observe strong sensitivity of the total reaction rate to small variations of the three-body part of the Li 2 Na interaction at short range, which we attribute to a relatively small number of open Li 2 ( a 3 Σ u + ) product channels populated in the reaction. This provides the first signature of highly non-universal dynamics seen in rigorous quantum reactive scattering calculations of an ultracold exothermic insertion reaction involving a polar alkali dimer molecule, opening up the possibility of probing microscopic interactions in atom+molecule collision complexes via ultracold reactive scattering experiments.
A fundamental question in the study of chemical reactions is how reactions proceed at a collision energy close to absolute zero. This question is no longer hypothetical: quantum degenerate gases of atoms and molecules can now be created at temperatures lower than a few tens of nanoKelvin. In this work we consider the benchmark ultracold reaction between, the most-celebrated ultracold molecule, KRb and K. For the first time we map out an accurate ab initio ground state potential energy surface of the KRbK complex in full dimensionality and report numerically exact quantum-mechanical reaction dynamics. The distribution of rotationally resolved rates is shown to be Poissonian. An analysis of the hyperspherical adiabatic potential curves explains this statistical character revealing a chaotic distribution for the short-range collision complex that plays a key role in governing the reaction outcome. We compare this with a lighter system with a smaller density of states (here the LiYbLi trimer) which displays random, and not chaotic, behavior.
computed potential energy surfaces are reported that include the two lowest-lying electronic states, their conical intersection, non-adiabatic couplings and an accurate long-range behavior. A numerically exact time-independent quantum dynamics method in hyperspherical coordinates is used to compute the elastic scattering cross sections, rate coefficients and collision lifetime spectrum. The quantum scattering calculations include all degrees of freedom and treat both electronic states and their non-adiabatic couplings using a two-state diabatic representation. The theoretically computed elastic rate coefficient is in good agreement with the recently reported experimental value. Significant non-adiabatic quantum interference effects are shown to originate from the unique properties of ultracold collisions and the geometric phase associated with the conical intersection. A high-resolution collision energy grid is used to investigate the origin of the experimentally reported long-lived 3-body collision complexes.