The creation of a gas of ultracold polar molecules with a high phase space density brings new possibilities beyond experiments with ultracold atomic gases. In particular, long-range, anisotropic, and tunable dipole-dipole interactions open the way for novel quantum gases, with applications including strongly correlated many-body systems, and ultracold chemistry. This thesis will present the final steps to complete control over both internal and external degrees of freedom of the molecule which allows us to control, and even completely suppress, the chemical reactions between molecules. First, the control over internal states has been achieved through coherent state transfer to the ro-vibronic ground state and coherent manipulations of the hyperfine and rotational states with microwave radiation. Second, external degrees of freedom are controlled by loading the gas into an optical lattice. With the molecules loaded into a one-dimensional lattice, the orientation of the molecular collisions is controlled by manipulating both internal (hyperfine states) and external (motional states in the direction of tight confinement) degrees of freedom. Most striking is that by preparing the molecules all in the lowest band of the lattice in the same internal state, the molecular collisions can only occur in a side-by-side" orientation, where the chemical reaction rate is suppressed by the repulsive dipole-dipole interactions. The chemical reaction can be suppressed completely by further constraining the motion in the trap in a strong 3D lattice. Here we see lifetimes longer than 20 s, limited by o-resonant light scattering. Finally, the ac polarizability of the molecules is explored and controlled. The different rotational states of the molecule have different polarizabilities and will experience a different trapping force in both the optical dipole trap or lattice. We show that there is a magic angle" between the quantization axis and the polarization of the trapping laser at which the polarizabilities of two different rotational states can be matched, eliminating dephasing and allowing for coherent manipulations between rotational states.
The creation of a gas of ultracold polar molecules with a high phase space density brings new possibilities beyond experiments with ultracold atomic gases. In particular, long-range, anisotropic, and tunable dipole-dipole interactions open the way for novel quantum gases, with applications including strongly correlated many-body systems, and ultracold chemistry. This thesis will present the final steps to complete control over both internal and external degrees of freedom of the molecule which allows us to control, and even completely suppress, the chemical reactions between molecules. First, the control over internal states has been achieved through coherent state transfer to the ro-vibronic ground state and coherent manipulations of the hyperfine and rotational states with microwave radiation. Second, external degrees of freedom are controlled by loading the gas into an optical lattice. With the molecules loaded into a one-dimensional lattice, the orientation of the molecular collisions is controlled by manipulating both internal (hyperfine states) and external (motional states in the direction of tight confinement) degrees of freedom. Most striking is that by preparing the molecules all in the lowest band of the lattice in the same internal state, the molecular collisions can only occur in a side-by-side" orientation, where the chemical reaction rate is suppressed by the repulsive dipole-dipole interactions. The chemical reaction can be suppressed completely by further constraining the motion in the trap in a strong 3D lattice. Here we see lifetimes longer than 20 s, limited by o-resonant light scattering. Finally, the ac polarizability of the molecules is explored and controlled. The different rotational states of the molecule have different polarizabilities and will experience a different trapping force in both the optical dipole trap or lattice. We show that there is a magic angle" between the quantization axis and the polarization of the trapping laser at which the polarizabilities of two different rotational states can be matched, eliminating dephasing and allowing for coherent manipulations between rotational states.
This thesis presents the development of a toolbox for the coherent control of ultracold polar molecules. Such systems of molecules promise the creation of long-lived, highly dipolar quantum gases with applications spanning the fields of quantum state controlled chemistry, quantum information, quantum simulation, and precision measurement. However, the addition of vibrational and rotational degrees of freedom leads to molecular systems being significantly more complex than their widely used atomic counterparts. In this work we demonstrate full control of the quantum state down to the hyperfine level of an optically trapped sample of ultracold bosonic 87Rb133 Cs molecules, and exploit that control to begin an investigation into the collision processes which take place in an ultracold molecular gas. We create a sample of up to ∼ 4000 optically trapped molecules in their rovibronic and hyperfine ground state. We characterise the molecules by measuring their temperature, binding energy, and molecule-frame electric dipole moment. We perform spectroscopy of the first rotationally excited state with hyperfine state resolution using microwaves to determine accurate values of rotational and hyperfine coupling constants. We use coherent π pulses to perform complete transfer population between selected hyperfine levels of the ground, first-excited, and second-excited rotational states. We investigate the effect of the off-resonant light of our optical dipole trap on the rotational and hyperfine structure of the molecules. Through a combination of high-resolution microwave spectroscopy and parametric heating measurements, we characterise the polarisability of the 87Rb133Cs molecule. We demonstrate that coupling between neighbouring hyperfine states manifests in rich structure with many avoided crossings in any rotational state other than the ground state. This coupling may be tuned by rotating the polarisation of the linearly polarised trapping light. Finally, we study the lifetime of polar bosonic 87Rb133Cs molecules in our 3D optical dipole trap. We examine the lifetime of the molecules as a function of dipole trap intensity, magnetic field, and hyperfine and rotational state. Despite the chemical stability of the 87Rb133 Cs molecule, we observe lifetimes of ∼1 s corresponding to 2-body decay rates close to the universal limit.
Ultracold polar molecules, because of their long-range, spatially anisotropic interactions, are a new quantum system in which to study novel many-body phenomena. In our lab, we have produced the first quantum gas of 40K87Rb polar molecules. These molecules were found to undergo exothermic chemical reactions, and this led to interesting studies of chemistry near absolute zero. By creating the molecules at individual sites of a 3D optical lattice, we completely suppress these chemical reactions, and the polar molecule gas becomes stable and lives for tens of seconds. This thesis documents our efforts to explore coherent, many-body phenomena resulting from long-range dipolar interactions in the lattice. By encoding a spin-1=2 system in the rotational states of the molecules, we were able to realize spin-exchange interactions based on a spin Hamiltonian, which is one of the first steps in studying quantum magnetism with polar molecules. While this study was the first realization of such coherent dipolar interactions with polar molecules in a lattice, its full potential was limited by the low lattice filling fractions. Using our ability to exquisitely control the initial atomic gas mixture, we loaded a Mott insulator of Rb and a band insulator of K into the lattice. This quantum synthesis approach led to significantly higher molecular filling fractions and represents the first fully connected system of polar molecules in an optical lattice. This low-entropy quantum gas of polar molecules opens the door to interesting quantum simulations, which should be attainable in the next generation of the experiment.
Ultracold polar molecular quantum gases promise to open new research directions ranging from the study of ultra-cold chemistry, precision measurements to novel quantum phase transitions. Based on the preparation of high-phase space density gases of polar KRb molecules [1–3], I will discuss the control of dipolar collisions and chemical reactions of polar molecules in a regime where quantum statistics, single scattering partial waves, and quantum threshold laws play a dominant role [4]. In particular, I will point out the crucial role of electric dipole-dipole interactions [5] and external confinement [6] in determining the chemical reaction rate. Finally, I will discuss prospects of reaching quantum degeneracy in bialkali samples of polar molecules and prospects for these systems as novel dipolar quantum many-body systems.
Ultracold polar molecular gases promise new directions and exciting appli-cations in precision measurements, ultracold chemistry, electric-field controlled collisions, dipolar quantum gases, and quantum information sciences. This the-sis presents experimental realization of a near quantum degenerate gas of polar molecules, where the phase-space density of the gas achieved is more than 10 or-ders of magnitude higher than previous results. The near quantum degenerate gas of polar molecules is created using two coherent steps. First, atoms in an ul-tracold gas mixture are converted into extremely weakly bound molecules near a Fano-Feshbach resonance. Second, the weakly bound molecules are transferred to the ro-vibronic ground state using a coherent two-photon Raman technique. The fact that these ground-state molecules are polar is confirmed with a spectroscopic measurement of the permanent electric dipole moment. Finally, manipulation of the molecular hyperfine state is demonstrated; this allows molecules to be pop-ulated in a single quantum state, in particular, the lowest energy state. With an ultracold gas of molecules, full control of molecular internal state, and electric field as a new handle, ultracold molecular collisions, including ultracold chemical reactions and dipolar collisions, are studied.
Ultracold molecules are expected to find applications in cold chemistry, quantum phases, precision measurements and quantum information. In this thesis three novel applications of cold molecules are studied. First the thesis presents a general method for coherent control of collisions between non-identical particles. It is shown that by preparing two alkali-metal atoms in a superposition of hyperfine states, the elastic-to-inelastic cross section ratio can be manipulated at ultracold temperatures by tuning laser parameters in the presence of a magnetic field. The static field is needed to induce quantum interference between scattering states. Extensions of this scheme for ultracold molecular reactive scattering are discussed. Second, the thesis describes rotational excitons and polarons in molecular ensembles trapped in optical lattices. Rotational excitons can be manipulated using static electric and magnetic fields. For a one-dimensional molecular array with substitutional impurities any localized exciton state can be delocalized by applying a suitable electric field. The electric field induces correlations between diagonal and off-diagonal disorder. It is also shown that the translational motion of polar molecules in an optical lattice can lead to phonons. The lattice dynamics and the phonon spectrum depend on the strength and orientation of a static electric field. An array of polar molecules in an optical lattice can be described by generalized polaron model with tunable parameters including diagonal and off-diagonal exciton-phonon interactions. It is shown that in a strong electric field the system is described by a generalized Holstein model, and at weak electric fields by the Su-Schrieffer-Heeger (SSH) model. The possibility of observing a sharp polaron transition in the SSH model using polar alkali-metal dimers is discussed. Finally, the thesis presents a method to generate entanglement of polar molecules using strong off-resonant laser pulses. Bipartite entanglement between alkali-metal dimers separated by hundreds of nanometers can be generated. Maximally entangled states can be prepared by tuning the pulse intensity and duration. A scheme is proposed to observe the violation of Bell’s inequality based on molecular orientation correlation measurements. It is shown that using a combination of microwave and off-resonant optical pulses, arbitrary tripartite and many-particle states can be prepared.
Studying ultracold chemical reactions with quantum state resolution reveals details of the reaction processes, especially with single quantum state preparation of the reactants and state-selective detection of reaction products. In this thesis, we investigate two main processes: KRb + KRb → K2 + Rb2 reactions, and Rb and KRb atom-molecule collisions. In the KRb bimolecular reaction, we demonstrate the preservation of quantum coherence in bimolecular reactions for the first time, which is surprising in a reaction considered to be largely chaotic. Additionally, we proposed a coherent control scheme to manipulate product yields across different product channels. These results represent a critical step toward probing quantum coherence and entanglement in the chemical reaction. In atom-molecule collisions between Rb and KRb, we discovered an exceptionally long-lived intermediate complex, KRb2, which can be photo-excited by trapping light. The observed complex lifetime was orders of magnitude longer than theoretical predictions, underscoring the limitations of the current theory. We further explored the dependence of complex lifetimes on the initial quantum states and external electric and magnetic fields, providing additional experimental benchmarks to guide future theoretical work. Separately, we found that inelastic collisions between hyperfine-excited Rb atoms and KRb molecules can lead to rotation excitation of KRb post-collision. By probing the product state distribution, the result suggests that mechanical angular momentum is coupled to the spins. Such couplings are too weak in the current theory models to explain the result. Moreover, our result contradicts state-of-the-art coupled-channel calculations. These suggest that some subtle effects, such as molecular vibration and conical intersections, play a critical role in the reaction dynamics. The final piece of the thesis describes the observation of resonant interaction between a Rydberg atom and an ensemble of polar molecules. Such hybrid quantum systems have been proposed for a wide range of applications. Our work provides an experimental demonstration of resonant dipolar interactions between Rydberg atoms and ultracold polar molecules, paving the way for the realization of hybrid systems for quantum computation and simulation.