We explore possible pathways for the creation of ultracold polar $\mathrm{NaK}$ molecules in their absolute electronic and rovibrational ground state starting from ultracold Feshbach molecules. In particular, we present a multichannel analysis of the electronic ground and $\text{K}(4p)+\text{Na}(3s)$ excited-state manifold of NaK, analyze the spin character of both the Feshbach molecular state and the electronically excited intermediate states and discuss possible coherent two-photon transfer paths from Feshbach molecules to rovibronic ground-state molecules. The theoretical study is complemented by the demonstration of stimulated Raman adiabatic passage from the $X{\phantom{\rule{0.16em}{0ex}}}^{1}{\ensuremath{\Sigma}}^{+}$($v=0$) state to the $a{\phantom{\rule{0.16em}{0ex}}}^{3}{\ensuremath{\Sigma}}^{+}$ manifold on a molecular beam experiment.
We explore possible pathways for the creation of ultracold polar NaK molecules in their absolute electronic and rovibrational ground state starting from ultracold Feshbach molecules. In particular, we present a multichannel analysis of the electronic ground and K(4p)+Na(3s) excited-state manifold of NaK, analyze the spin character of both the Feshbach molecular state and the electronically excited intermediate states and discuss possible coherent two-photon transfer paths from Feshbach molecules to rovibronic ground-state molecules. The theoretical study is complemented by the demonstration of stimulated Raman adiabatic passage from the X1\ensuremathΣ+(v=0) state to the a3\ensuremathΣ+ manifold on a molecular beam experiment.
One possibility for the creation of ultracold, high phase space density quantum gases of molecules in the rovibronic ground state relies on first associating weakly-bound molecules from quantum-degenerate atomic gases on a Feshbach resonance and then transferring the molecules via several steps of coherent two-photon stimulated Raman adiabatic passage (STIRAP) into the rovibronic ground state. Here, in ultracold samples of Cs2 Feshbach molecules produced out of ultracold samples of Cs atoms, we observe several optical transitions to deeply-bound rovibrational levels of the excited 0(u)+ molecular potentials with high resolution. At least one of these transitions, although rather weak, allows efficient STIRAP transfer into the deeply-bound vibrational level (see text for symbols)v = 73 > of the singlet X1 sigma(g)+ ground state potential, as recently demonstrated (J. G. Danzl, E. Haller, M. Gustavsson, M. J. Mark, R. Hart, N. Bouloufa, O. Dulieu, H. Ritsch, and H.-C. Nägerl, Science, 2008, 321, 1062). From this level, the rovibrational ground state (see text for symbols)v = 0, J = 0 > can be reached with one more transfer step. In total, our results show that coherent ground state transfer for Cs2 is possible using a maximum of two successive two-photon STIRAP processes or one single four-photon STIRAP process.
We report on high-resolution spectroscopy of ultracold fermionic 23 Na 40 K Feshbach molecules, and identify a two-photon pathway to the rovibrational singlet ground state via a resonantly mixed B 1 Π ∼ c 3 Σ + intermediate state.Photoassociation in a 23 Na-40 K atomic mixture and one-photon spectroscopy on 23 Na 40 K Feshbach molecules reveal about 20 vibrational levels of the electronically excited c 3 Σ + state.Two of these levels are found to be strongly perturbed by nearby B 1 Π levels via spinorbit coupling, resulting in additional lines of dominant singlet character in the perturbed complex. The dominantly singlet level is used to locate the absolute rovibrational singlet ground state v J X 0, 0via Autler-Townes spectroscopy.We demonstrate coherent two-photon coupling via dark state spectroscopy between the predominantly triplet Feshbach molecular state and the singlet ground state.Its binding energy is measured to be 5212.0447(1)cm -1 , a thousand-fold improvement in accuracy compared to previous determinations.In their absolute singlet ground state, 23 Na 40 K molecules are chemically stable under binary collisions and possess a large electric dipole moment of 2.72 Debye.Our work thus paves the way towards the creation of strongly dipolar Fermi gases of NaK molecules.
This thesis reports on the construction of a novel experimental apparatus to create an ultracold sample of chemical stable 23Na40K polar molecules at their absolute ground states. The long range nature of the dipolar interactions between the ground state molecules, is expected to facilitate to observe new quantum many-body states and to simulate prototypical lattice spin models for exploring quantum magnetism and high Tc superconductivity. The experimental procedures are presented in this thesis including: trapping and cooling 23Na and $ ^{40}\rm{K}$ atoms to quantum degeneracy, associating weakly bound state molecules with Feshbach resonances, and transferring the Feshbach molecules to the rovibrational ground states via stimulated Raman adiabatic passage. As a result, successful transfer has been demonstrated in our experiment with a single-path transfer efficiency ≃60% via a hyperfine non-resolved intermediate state ∣d3Π,ν=5,J=1,Ω=1⟩. In addition, a perturbative theoretical study on the Fermi liquid properties of a single-component weakly-interacting two dimensional dipolar fermions with dipole moments d oriented perpendicularly to the plane of their translational motion is presented in the thesis. When the dipole moments are tilted with respect to the translational plane, the effect of anisotropic interaction appears, and collective excitations in the collisionless regime are studied in this configuration. Furthermore, stable dilute supersolid states with two-dimensional bosonic dipoles are predicted to exist with an additional three-body repulsive contact interaction. These novel quantum effects should be accessible experimentally once the NaK ground state molecules reach quantum degeneracy by further evaporative cooling.
We study the rovibronic transitions in NaK 2 between its electronic ground state 1 2 A ′ and its second excited state 3 2 A ′ , to identify possible pathways for the creation of ultracold ground-state triatomic molecules. Our methodology relies on the computation of potential energy surfaces and transition dipole moment surfaces for the relevant electronic states using methods. Rovibrational energy levels and wave functions are determined using the discrete variable representation approach. A double-well structure of the potential energy surface is identified for both states, and the related transition strengths between the rovibrational levels are derived. Our calculations show that the formation of ultracold ground-state NaK 2 molecules is expected when starting from an excited electronic state of NaK 2 , which can be created by photoassociation of NaK and K, as observed by optical means by Cao, [].
Ultracold bialkali polar molecules play a leading part at the frontline of quantum physics. They recently attract a lot of attention in the field of ultracold quantum chemistry, quantum many-body physics and quantum simulations. The key for their success is the rich internal level structure with rotational and vibrational degrees of freedom and their large electric dipole moments. Still, only a handful of molecular species are available at ultracold temperatures until now, although it is highly desirable to produce new molecular species to further expand the range of applications. Besides direct laser cooling methods for molecules, the assembly of heteronuclear ground-state molecules from ultracold atomic mixtures is the most promising approach for the creation of polar molecules. It includes the formation of weakly bound Feshbach molecules from the diatomic mixture and the subsequent two-photon stimulated Raman adiabatic passage (STIRAP) transfer to the rovibrational ground state. This creation strategy has been successfully demonstrated for the first time in the pioneering experiments at JILA with ultracold 40K87Rb molecules. Since then, only a few more molecular species from different alkali atoms have been created, namely 6Li23Na, 23Na40K, 23Na87Rb and 87Rb133Cs. In this thesis, I report the successful creation of a new species of ultracold polar ground-state molecules: 23Na39K. Starting from an ultracold mixture of bosonic 23Na and 39K atoms, weakly bound molecules are created. For this purpose, a Feshbach resonance in a high angular momentum scattering channel is chosen, experimentally identified and characterized. Close to this resonance the weakly bound Feshbach molecules are formed using resonant radio frequency radiation. For the two-photon ground-state transfer, a unique, highly specialized two-color laser system is designed and realized. It is used for one- and two-photon spectroscopy to identify the relevant transitions for the ground-state transfer. Based on the obtained data, a local model of the singlet-triplet mixed excited state manifolds is developed, with which the hyperfine structure and the magnetic field dependence is predicted with high accuracy. According to these findings, a suitable pathway to a single hyperfine ground state is chosen considering selection rules and experimental conditions such as laser polarization and beam alignment. To precisely determine the two-photon resonance condition for STIRAP, electromagnetically induced transparency measurements are performed. The ground-state transfer is then performed using STIRAP. The experimental findings regarding the STIRAP are successfully supported theoretically by a model based on a five-level master equation. The pure molecular gas shows evidence for two-body dominated loss mechanisms, such as sticky four-body collisions. The molecule-atom mixture of 23Na39K+39K reveals an unexpectedly low loss rate coefficient although sticky three-body collisions are assumed to occur. This behavior demands further investigations regarding different hyperfine collisional chan-nels and magnetic field regions.
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.