Ultracold diatomic molecules have achieved significant breakthroughs in recent years, enabling the exploration of quantum chemistry, precision measurements, and strongly correlated many-body physics. Extending ultracold molecular complexity to polyatomic molecules, such as triatomic and tetratomic molecules, has attracted considerable interest. However, the realization of ultracold polyatomic molecules remains technically challenging due to their complex energy-level structures. While only a few experiments have successfully demonstrated the formation of polyatomic molecules by magnetoassociation or electroassociation, here we present the first step toward producing tetratomic molecules through the development of a microwave association technique combined with microwave dressing. When the two lowest rotational states of the molecules are dressed by a microwave field, weakly bound tetramer states emerge in the entrance channel with free dark excited states $\ket{0}$ and a dressed state $\ket{+}$. The spectroscopy of these weakly bound tetramers is probed by another microwave field that drives transitions from the populated dressed states $\ket{+}$. By precisely discriminating the complex hyperfine structure of the dark excited level $\ket{0}$ from the dressed-state spectroscopy, the binding energy of the tetratomic molecules is measured and characterized. Our work contributes to the understanding of complex few-body physics within a system of microwave-dressed molecules and may open an avenue toward the creation and control of ultracold polyatomic molecules.
Ultracold diatomic molecules have achieved significant breakthroughs in recent years, enabling the exploration of quantum chemistry, precision measurements, and strongly correlated many-body physics. Extending ultracold molecular complexity to polyatomic molecules, such as triatomic and tetratomic molecules, has attracted considerable interest. However, the realization of ultracold polyatomic molecules remains technically challenging due to their complex energy-level structures. While only a few experiments have successfully demonstrated the formation of polyatomic molecules by magnetoassociation or electroassociation, here we present the first step toward producing tetratomic molecules through the development of a microwave association technique combined with microwave dressing. When the two lowest rotational states of the molecules are dressed by a microwave field, weakly bound tetramer states emerge in the entrance channel with free dark excited states ∣0⟩ and a dressed state ∣+⟩. The spectroscopy of these weakly bound tetramers is probed by another microwave field that drives transitions from the populated dressed states ∣+⟩. By precisely discriminating the complex hyperfine structure of the dark excited level ∣0⟩ from the dressed-state spectroscopy, the binding energy of the tetratomic molecules is measured and characterized. Our work contributes to the understanding of complex few-body physics within a system of microwave-dressed molecules and may open an avenue toward the creation and control of ultracold polyatomic molecules.
Abstract Ultracold polyatomic molecules offer opportunities 1 in cold chemistry 2,3 , precision measurements 4 and quantum information processing 5,6 , because of their rich internal structure. However, their increased complexity compared with diatomic molecules presents a challenge in using conventional cooling techniques. Here we demonstrate an approach to create weakly bound ultracold polyatomic molecules by electroassociation 7 (F.D. et al., manuscript in preparation) in a degenerate Fermi gas of microwave-dressed polar molecules through a field-linked resonance 8–11 . Starting from ground-state NaK molecules, we create around 1.1 × 10 3 weakly bound tetratomic (NaK) 2 molecules, with a phase space density of 0.040(3) at a temperature of 134(3) nK, more than 3,000 times colder than previously realized tetratomic molecules 12 . We observe a maximum tetramer lifetime of 8(2) ms in free space without a notable change in the presence of an optical dipole trap, indicating that these tetramers are collisionally stable. Moreover, we directly image the dissociated tetramers through microwave-field modulation to probe the anisotropy of their wavefunction in momentum space. Our result demonstrates a universal tool for assembling weakly bound ultracold polyatomic molecules from smaller polar molecules, which is a crucial step towards Bose–Einstein condensation of polyatomic molecules and towards a new crossover from a dipolar Bardeen–Cooper–Schrieffer superfluid 13–15 to a Bose–Einstein condensation of tetramers. Moreover, the long-lived field-linked state provides an ideal starting point for deterministic optical transfer to deeply bound tetramer states 16–18 .
A theoretical model is proposed for the formation of ultracold ground-state triatomic molecules in weakly bound energy levels. The process is driven by the electric component of a microwave field, which induces the association of an ultracold atom colliding with an ultracold diatomic molecule. This model is exemplified using K 39 atoms and Na 23 K 39 molecules, both in their ground states, a scenario of experimental relevance. The model assumes that the dynamics of the association are dominated by the long-range van der Waals interaction between K 39 and Na 23 K 39 . The electric microwave association mechanism relies on the intrinsic electric dipole moment of Na 23 K 39 , which drives transitions between its lowest rotational levels ( j =0 and j =1). The energies of the uppermost triatomic energy levels are computed by numerically solving coupled Schrödinger equations using the Mapped Fourier Grid Hamiltonian method. Measurable association rates are derived within the framework of a perturbative approach. This method of electric microwave association provides an alternative to atom-molecule association via magnetic Feshbach resonances for forming ultracold, deeply bound triatomic molecules, and is applicable to a wide range of polar diatomic molecules.
The presence of electric or microwave fields can modify the long-range forces between ultracold dipolar molecules in such a way as to engineer weakly bound states of molecule pairs. These so-called field-linked states [A. V. Avdeenkov and J. L. Bohn, Phys. Rev. Lett. 90, 043006 (2003).PRLTAO0031-900710.1103/PhysRevLett.90.043006; L. Lassablière and G. Quéméner, Phys. Rev. Lett. 121, 163402 (2018).PRLTAO0031-900710.1103/PhysRevLett.121.163402], in which the separation between the two bound molecules can be orders of magnitude larger than the molecules themselves, have been observed as resonances in scattering experiments [X.-Y. Chen et al., Nature (London) 614, 59 (2023).NATUAS0028-083610.1038/s41586-022-05651-8]. Here, we propose to use them as tools for the assembly of weakly bound tetramer molecules, by means of ramping an electric field, the electric-field analog of magnetoassociation in atoms. This ability would present new possibilities for constructing ultracold polyatomic molecules.
The assembly and coherent control of ultracold molecules have opened new horizons in quantum science with applications in ultracold chemistry, quantum information, quantum simulation, precision metrology and fundamental physics. While considerable progress has been achieved in controlling diatomic molecules at ultracold temperatures, extending to atom-diatom collisions and triatomic systems introduces additional internal structure, anisotropy, and interaction complexity, enabling access to many-body phenomena. This dissertation presents a detailed theoretical study on the production and stabilization of ultracold alkali-metal triatomic molecules, with a particular focus on the NaK2 molecular species. First, long-range photoassociation in ultracold NaK(X^1Σ+) + K(4s) mixtures is investigated near the molecular transition X^1Σ+ → b^3Π. Photoassociation rates into weakly bound trimers in the electronically excited 3^2A' state are evaluated under experimentally relevant conditions. The calculated photoassociation rates indicate experimentally feasible and spectrally selective routes for detecting ultracold atom–diatom photoassociation resonances, while suppressing competing diatomic loss channels. Second, a microwave-assisted association mechanism is introduced for coherently binding ultracold atoms and polar molecules into weakly bound triatomic molecules on the ground-state 1^2A' potential energy surface. This process relies on the interaction between the electric component of the microwave field and the permanent electric dipole moment of the NaK molecule. In the presence of the anisotropic atom–diatom potential, which couples the molecular rotation to the relative angular motion, the microwave field can drive transitions from scattering states to weakly bound trimer states entirely in the electronic ground-state of the triatomic molecule, without involving spontaneous emission. This process is therefore intrinsically coherent and particularly suited to closed-shell polar molecules for which magnetically tunable Feshbach resonances are weak or absent. Finally, candidate pathways toward coherent population transfer to the absolute rovibronic ground state of NaK2 are explored using bridge states belonging to the excited 3^2A' electronic state, such as those identified in [Ref.1]. The relevant potential energy surfaces, transition dipole moments, and rovibrational structures are analyzed, revealing favorable conditions for future stimulated Raman adiabatic passage scheme. The theoretical modeling combines high-level electronic-structure calculations with nuclear-motion methods across multiple energy and length scales. Three-dimensional potential energy surfaces and electronic transition dipole moment surfaces were obtained from ab initio multireference configuration interaction calculations employing effective-core pseudopotentials and core-polarization potentials. Nuclear motion was treated using coupled-channel methods for describing weakly bound states and discrete variable representation methods for deeply bound rovibrational states. The resulting wavefunctions were subsequently used to evaluate Franck–Condon factors, photo- and microwave association rates, and transition strengths relevant to experimental implementation. Overall, this dissertation provides an extensive theoretical framework for the formation, detection and ground-state stabilization of ultracold NaK2 trimers. Reference: [1] J. Cao, B.-Y. Wang, H. Yang, Z.-J. Fan, Z. Su, J. Rui, B. Zhao, and J.-W. Pan, “Observation of photoassociation resonances in ultracold atom-molecule collisions,” Phys. Rev. Lett., vol. 132, p. 093403, 2024.
In recent years, there has been notable progress in the preparation and control of ultracold gases of diatomic molecules. The next experimental challenge is the production of ultracold polyatomic molecular gases. Here, we report the creation of an ultracold gas of 23 Na 40 K 2 triatomic molecules from a mixture of ground-state sodium-23–potassium-40 ( 23 Na 40 K) molecules and potassium-40 ( 40 K) atoms. The triatomic molecules were created by adiabatic magneto-association through an atom–diatomic molecule Feshbach resonance. We obtained clear evidence for the creation of triatomic molecules by directly detecting them using radio-frequency dissociation. Approximately 4000 triatomic molecules with a high-peak phase-space density of 0.05 could be created. The ultracold triatomic molecules can serve as a launchpad to probe the three-body potential energy surface and may be used to prepare quantum degenerate triatomic molecular gases.
We investigate the static and dynamic properties of tetratomic molecules formed by two microwave-shielded polar molecules across field-linked resonances. In particular, we focus on two-body physics and experimental techniques unexplored in the recent experiment [X.-Y. Chen {\it et al}., Nature {\bf626}, 283 (2024)]. We show that, compared to the lowest tetramer state, higher tetramer states typically have longer lifetimes, which may facilitate a further cooling of tetramer gases towards quantum degeneracy. To detect tetramers, we identify the distinctive time-of-flight images from ramp dissociation, which can be observed by lowering the ramp rate of the microwave. Remarkably, in the modulational dissociation of tetramers, we find that multi-photon processes induce dissociation even below the threshold modulation frequency when the modulation amplitude is sufficiently high. Given the universal form of the inter-molecular potential for microwave-shielded polar molecules, our results also apply to other molecular gases widely explored in recent experiments.