We have performed three theoretical simulations relevant for describing collisions among laser-cooled silver atoms and for the formation of Ag 2 molecules from these colliding atoms. Firstly, we determined the relativistic electronic structure of Ag 2 molecules in ground and low-lying excited states. Secondly, we computed rotational and vibrational levels of the ground and excited electronic states as well as rovibrationally averaged electric transition dipole moments. Using this knowledge, we analyzed a simplified quantum-mechanical model of the one-photon photoassociation process to form electronically excited Ag 2 from microkelvin Ag atoms and make predictions for lineshapes and saturation effects as functions of laser frequency and intensity. Finally and thirdly, we performed coupled-channels calculations, numerical solutions of sets of coupled radial Schrödinger equations of ultracold ground-state Ag collisions in an external magnetic field. These calculations include the effects of two Born-Oppenheimer potentials as well as hyperfine Fermi-contact and Zeeman interactions. We discuss the expected range of s -wave scattering lengths as well as strengths and distribution of Fano-Feshbach resonances as a function of the magnetic-field strength for the Ag 107 and Ag 109 isotopes. We highlight the periodicity of the scattering length with small changes in the depths of the Born-Oppenheimer potentials. The Fano-Feshbach resonances can be used to magneto-associate ultracold Ag atoms into weakly bound ground-state Ag 2 dimers.
We have performed three theoretical simulations relevant for describing collisions among laser-cooled silver atoms and for the formation of Ag 2 molecules from these colliding atoms. Firstly, we determined the relativistic electronic structure of Ag 2 molecules in ground and low-lying excited states. Secondly, we computed rotational and vibrational levels of the ground and excited electronic states as well as rovibrationally averaged electric transition dipole moments. Using this knowledge, we analyzed a simplified quantum-mechanical model of the one-photon photoassociation process to form electronically excited Ag 2 from microkelvin Ag atoms and make predictions for lineshapes and saturation effects as functions of laser frequency and intensity. Finally and thirdly, we performed coupled-channels calculations, numerical solutions of sets of coupled radial Schrödinger equations of ultracold ground-state Ag collisions in an external magnetic field. These calculations include the effects of two Born-Oppenheimer potentials as well as hyperfine Fermi-contact and Zeeman interactions. We discuss the expected range of s -wave scattering lengths as well as strengths and distribution of Fano-Feshbach resonances as a function of the magnetic-field strength for the Ag 107 and Ag 109 isotopes. We highlight the periodicity of the scattering length with small changes in the depths of the Born-Oppenheimer potentials. The Fano-Feshbach resonances can be used to magneto-associate ultracold Ag atoms into weakly bound ground-state Ag 2 dimers.
Abstract Molecules with unstable isotopes often contain heavy and deformed nuclei and thus possess a high sensitivity to parity-violating effects, such as the Schiff moments. Currently the best limits on Schiff moments are set with diamagnetic atoms. Polar molecules with quantum-enhanced sensing capabilities, however, can offer better sensitivity. In this work, we consider the prototypical 223Fr107Ag molecule, as the octupole deformation of the unstable 223Fr francium nucleus amplifies the nuclear Schiff moment of the molecule by two orders of magnitude relative to that of spherical nuclei and as the silver atom has a large electron affinity. To develop a competitive experimental platform based on molecular quantum systems, 223Fr atoms and 107Ag atoms have to be brought together at ultracold temperatures. That is, we explore the prospects of forming 223Fr107Ag from laser-cooled Fr and Ag atoms. We have performed fully relativistic electronic-structure calculations of ground and excited states of FrAg that account for the strong spin-dependent relativistic effects of Fr and the strong ionic bond to Ag. In addition, we predict the nearest-neighbor densities of magnetic-field Feshbach resonances in ultracold 223Fr + 107Ag collisions with coupled-channel calculations. These resonances can be used for magneto-association into ultracold, weakly-bound FrAg. We also determine the conditions for creating 223Fr107Ag molecules in their absolute ground state from these weakly-bound dimers via stimulated Raman adiabatic passage using our calculations of the relativistic transition electric dipole moments.
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 this dissertation, I present ab initio theoretical results on cold and ultra-cold collision of atomic and molecular systems with magnetic and electric dipole moments. The collisions of different isotopes of maximally spin-polarized chromium atoms (52Cr and 53Cr), alkali-metal atom (Rb) - chromium atom, and magnetically trapped hydroxide (OH) with cold supersonic helium beam are considered in this thesis. Spin-changing cross sections and rate constants in Cr-Cr isotopic collision in the presence of a magnetic field are calculated by propagating a set of multichannel equations in the field. The coupling between dipole-dipole allowed and hyperfine channels are included. The short range electrostatic interactions between atoms and atom-molecule are represented with highly-accurate Born-Oppenheimer (BO) potential energy curves. Due to the large spin multiplicity in Cr-Cr and Rb-Cr interactions, more than the usual singlet and triplet channels are obtained. The long-range van der Waals (vdW) interactions between atoms are calculated, for Cr, by including accurate transition frequencies, discrete dipole matrix elements, and photoionization continuum oscillator strengths, and for Rb, using published dynamic polarizabilities. The vdW coefficients for Cr-Cr and Rb-Cr are obtained. In the cold collision regime, I investigate the influence of angular momentum shape resonances on the elastic and inelastic (loss channel) rate coefficients, and when the Zeeman relaxation, resulting in the loss of atoms from the trap, dominates elastic collision. Dipolar collisions are crucial to achieving quantum degeneracy. Magnetically tuned Fano-Feshbach closed-channel resonances are used to obtain zero-energy scattering lengths in comparison with observation of trap loss. In bosonic chromium collisions, resonances appear due only to dipolar interaction. The interplay between hyperfine and dipolar resonances in mixed-species Cr-Cr and Rb-Cr collisions is studied. In Rb-Cr, it is found that the molecule has broken symmetry and therefore contains a large permanent electric dipole moment in the ground state. A recent collisional experiment at JILA of a supersonic helium beam with a magnetically trapped OH radical found the onset of a quantum threshold in the total OH loss rate. Using ab initio BO energy surfaces, I calculated the spin-changing collisions which removed OH from the trap. Only after including the effect of the trapping potential on the collision dynamics, some agreement with observation was found. ^
Assembly of ultracold polar molecules containing silver (Ag) from laser-cooled atoms requires knowledge of the dynamic polarizabilities of Ag at convenient laser wavelengths. We present calculations and analysis of the energies and electric-dipole dc and ac polarizabilities of the low-lying states of neutral Ag. Calculations of the properties of the 4d10x states, where x=5s,6s,7s,5p,6p,7p,5d,6d, and 4f, are performed using the linearized coupled cluster single-double method. The properties of the 4d95s22D5/2,3/2 states are obtained within the framework of configuration interaction with 11 and 17 electrons in the valence field. We analyze the different contributions to the polarizabilities and estimate the uncertainties of our predictions.
The susceptibility of ultracold gases to precise manipulation via external fields makes them ideal systems to study fundamental quantum mechanical phenomena. Various regimes, which are not possible to reach in condensed matter or nuclear physics, can be probed with these quantum gases. Especially the tunability of the interactions and confining potentials make that these ultracold gases offer unique possibilities to explore and study universal behavior. The tunability of the dominant two-body interactions in dilute ultracold atomic gases stems from the presence of Feshbach resonances. Via these resonances pairs of ultracold atoms can be associated to form ultracold molecules. In fact, measurements of Feshbach resonance positions can be used to reveal part of the underlying molecular structure. Vica versa, accurate molecular Born-Oppenheimer potentials can be used as input for full numerical coupled-channels calculations to reliably predict Feshbach resonances. For most of the heteronuclear mixtures currently studied however, the relevant molecular potentials are not accurate enough. As the coupled-channels method is often too elaborate and too time consuming to be used to fit the measured data to enable the construction of more accurate potentials, a need for accurate models which complement this established method is created. In this thesis we have developed a simplified model for resonant scattering of two ultracold atoms which fulfills this need. The asymptotic bound-state model (ABM) is a hierarchical model which can be systematically increased in complexity and accuracy. In its most simple form, the ABM only needs two parameters to predict the position and strength of Feshbach resonances: Two binding energies corresponding to the least bound state of the two molecular potentials involved. We demonstrate that this model, although it is solely based on bound states, can incorporate threshold effects. Additionally, the model can be extended to include: Multiple vibrational levels, overlapping resonances, and magnetic dipole-dipole interactions. This versatile model allows for a description of Feshbach resonances in a large variety of systems without accurate knowledge of the relevant molecular Born-Oppenheimer potentials. Being computationally light, the ABM can be used to analyze measurements of Feshbach resonances and hereby expose the basic underlying molecular structure. Additionally, the ABM is well suited to map out all available Feshbach resonances in a system. This ability is particularly useful when an optimal resonance is required for a certain experiment. For the 6Li-40K mixture we have utilized this ability to experimentally observe a strong Feshbach resonance which offers promising perspectives to reach the strongly interacting universal regime in a mass-imbalanced Fermi gas. By analyzing the various inelastic decay processes and the accuracy of the ab initio Born-Oppenheimer potentials, we predict a strong resonance in a mixture of metastable bosonic and fermionic helium atoms. For the homonuclear (bosonic as well as fermionic) helium gas we do not find strong resonances. For an ultracold gas of 40K atoms, an elaborate combined theoretical and experimental effort is presented to map out the Feshbach resonance structure. On the experimental side we observed 36 Feshbach resonances, 31 of which where observed for the first time. These observations are in excellent agreement with coupled-channels calculations which use unmodified Born-Oppenheimer potentials as input. On the theoretical side, we present a comparison between different simplified models of resonance scattering and the full numerical coupled-channels calculations. We have developed the resonant state model (RSM) to describe the resonant scattering of two ultracold atoms. This model is founded on resonant states, the natural (eigen) frequencies of the two-body system, and their non-trivial properties. Threshold effects are implicitly build into the RSM. The RSM can describe the effect of the continuum of scattering states, states which are neglected in the ABM, on the position and strength of a Feshbach resonance by only a few resonant states. Especially when a low-energy resonance is embedded in the continuum of scattering states, the effect of these states on the Feshbach resonance cannot be neglected. The RSM can be viewed as the natural generalization of the ABM. As the RSM can be based on just a few resonant states, it retains the computational simplicity of the ABM. Using the tunability of two-body interactions induced by a Feshbach resonance, we describe a crossover for a rotating Fermi gas between two strongly-correlated many-body states. We demonstrate that the correlation induced long-range interaction will shift the crossover with respect to the non-rotating case.
State-of-the-art ab initio techniques have been applied to compute the potential energy curves for the SrYb molecule in the Born-Oppenheimer approximation for the electronic ground state and the first fifteen excited singlet and triplet states. All the excited state potential energy curves were computed using the equation of motion approach within the coupled-cluster singles and doubles framework and large basis-sets, while the ground state potential was computed using the coupled cluster method with single, double, and noniterative triple excitations. The leading long-range coefficients describing the dispersion interactions at large interatomic distances are also reported. The electric transition dipole moments have been obtained as the first residue of the polarization propagator computed with the linear response coupled-cluster method restricted to single and double excitations. Spin-orbit coupling matrix elements have been evaluated using the multireference configuration interaction method restricted to single and double excitations with a large active space. The electronic structure data were employed to investigate the possibility of forming deeply bound ultracold SrYb molecules in an optical lattice in a photoassociation experiment using continuous-wave lasers. Photoassociation near the intercombination line transition of atomic strontium into the vibrational levels of the strongly spin-orbit mixed b(3)Σ(+), a(3)Π, A(1)Π, and C(1)Π states with subsequent efficient stabilization into the v'' = 1 vibrational level of the electronic ground state is proposed. Ground state SrYb molecules can be accumulated by making use of collisional decay from v'' = 1 to v'' = 0. Alternatively, photoassociation and stabilization to v'' = 0 can proceed via stimulated Raman adiabatic passage provided that the trapping frequency of the optical lattice is large enough and phase coherence between the pulses can be maintained over at least tens of microseconds.