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Physical Chemistry Chemical Physics

A neural network potential energy surface for the Li + LiNa → Li 2 + Na reaction and quantum dynamics study from ultracold to thermal energies

Bayaer Buren

Published Jan 1, 2023• 3 citations
Publisher

Abstract

, 124303), which indicates that the dynamics of the ultracold Li + LiNa reaction can be well described by the SQM approach. The time-dependent wave packet calculations are performed for the Li + LiNa reaction at thermal energies, and the characteristic of differential cross-sections confirms that the reaction follows the complex-forming reaction mechanism.

DOI
10.1039/d3cp01753b

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, 124303), which indicates that the dynamics of the ultracold Li + LiNa reaction can be well described by the SQM approach. The time-dependent wave packet calculations are performed for the Li + LiNa reaction at thermal energies, and the characteristic of differential cross-sections confirms that the reaction follows the complex-forming reaction mechanism.
The ultracold reaction offers a unique opportunity to elucidate the intricate microscopic mechanism of chemical reactions, and the Na 2 Li system serves as a pivotal reaction system in the investigation of ultracold reactions. In this work, a high-precision potential energy surface (PES) of the Na 2 Li system is constructed based on high-level ab initio energy points and the neural network (NN) method, and a proper asymptotic functional form is adopted for the long-range interaction, which is suitable for the study of cold or ultracold collisions. Based on the new NN PES, the dynamics of the Li + Na 2 ( v = 0, j = 0) → Na + NaLi reaction are studied in the collision energy range of 10 –7 to 80 cm –1 . In the high collision energy range of 8 to 80 cm –1, the dynamics of the reaction is studied using the time-dependent wave packet method and the statistical quantum mechanical (SQM) method. Comparing the results of the two methods, it is found that the SQM method provides a rough description of the product ro-vibrational state distribution but overestimates the integral cross-section values. With the decrease of collision energy, the reaction differential cross section gradually changes from forward–backward symmetric scattering to predominant forward scattering. In the low collision energy range from 10 –7 to 8 cm –1, the SQM method is used to study the reaction dynamics, and the rate constant in the Wigner threshold region is estimated to be 2.87 × 10 –10 cm 3 /s.
The LiNa2 reactive system has recently received great attention in the experimental study of ultracold chemical reactions, but the corresponding theoretical calculations have not been carried out. Here, we report the first globally accurate ground-state LiNa2 potential energy surface (PES) using a Gaussian process model based on only 1776 actively selected high-level ab initio training points. The constructed PES had high precision and strong generalization capability. On the new PES, the quantum dynamics calculations on the Li(2S) + Na2(v = 0, j = 0) → LiNa + Na reaction were carried out in the 0.001–0.01 eV collision energy range using an improved time-dependent wave packet method. The calculated results indicate that this reaction is dominated by a complex-forming mechanism at low collision energies. The presented dynamics data provide guidance for experimental research, and the newly constructed PES could be further used for ultracold reaction dynamics calculations on this reactive system.
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.
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 potential energy surface for the lowest quartet electronic state ((4)A(')) of lithium trimer is developed and used to study spin-polarized Li+Li(2) collisions at ultralow kinetic energies. The potential energy surface allows barrierless atom exchange reactions. Elastic and inelastic cross sections are calculated for collisions involving a variety of rovibrational states of Li(2). Inelastic collisions are responsible for trap loss in molecule production experiments. Isotope effects and the sensitivity of the results to details of the potential energy surface are investigated. It is found that for vibrationally excited states, the cross sections are only quite weakly dependent on details of the potential energy surface.
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.