The first part of this project involved continued development of theoretical models of diatomic molecular electronic level structure for application to the production of ultracold diatomic molecules via photoassociation. Recently, there has been considerable interest in producing molecules at the temperatures achieved for laser-cooled atoms, for applications to "coherent chemistry," studies of molecule-atom and molecule-molecule interactions. Bose condensates of molecules and for quantum computing. It is advantageous to produce cold molecules from laser-cooled atoms. but this requires an accurate model of the energy level structure near the dissociation limit for excited atoms, and for other intermediate states. With this in mind. we have modeled experimental photoassociation data from Rb2. spectroscopic data on the lowest excited states of Na2, and hyperfine structure of the lowest triplet state of Cs2. The second part involved continued development of experimental techniques for intense atomic beam collimation using a bichromatic laser field. We solved the equations for evolution of atoms in such a laser field, expressed the results in the form of trajectories on the Bloch sphere for a two-level atoms, and then used these results to design and perform efficient atomic beam reflection experiments. At the same time, we are developing methods to use these highly collimated beams of metastable helium atoms for precision lithography, using sensitized surfaces.
The first part of this project involved continued development of theoretical models of diatomic molecular electronic level structure for application to the production of ultracold diatomic molecules via photoassociation. Recently, there has been considerable interest in producing molecules at the temperatures achieved for laser-cooled atoms, for applications to "coherent chemistry," studies of molecule-atom and molecule-molecule interactions. Bose condensates of molecules and for quantum computing. It is advantageous to produce cold molecules from laser-cooled atoms. but this requires an accurate model of the energy level structure near the dissociation limit for excited atoms, and for other intermediate states. With this in mind. we have modeled experimental photoassociation data from Rb2. spectroscopic data on the lowest excited states of Na2, and hyperfine structure of the lowest triplet state of Cs2. The second part involved continued development of experimental techniques for intense atomic beam collimation using a bichromatic laser field. We solved the equations for evolution of atoms in such a laser field, expressed the results in the form of trajectories on the Bloch sphere for a two-level atoms, and then used these results to design and perform efficient atomic beam reflection experiments. At the same time, we are developing methods to use these highly collimated beams of metastable helium atoms for precision lithography, using sensitized surfaces.
Quantum gases of diatomic molecules are many body systems that offer unprecedented control over their intrinsic long and short range interactions. This is due to the unique nature of the interactions between molecules, which can be much stronger than those in magnetic atoms and which can be tuned independently through external electromagnetic fields. As a result, diatomic molecules enable both the exploration of novel supersolid states and the creation of dipole dominated and self assembled quantum solids. The molecular properties and internal structure of calcium monofluoride (CaF) make it a promising candidate molecule for the realization of several kinds of strongly correlated quantum systems, such as strongly dipolar Bose Einstein condensates, quantum crystals and arrays of molecules in optical tweezers. This dissertation summarizes the first steps towards the realization of such systems using directly laser cooled CaF molecules. The two major experimental steps which are summarized in this thesis are cryogenic buffer gas cooling and transversal laser cooling of CaF molecules. For the first achievement, cryogenic buffer gas cooling, it is important to observe that CaF molecules are radicals and therefore do not exist in a stable gas phase. As a result, the production of a beam of molecules requires a cryogenic buffer gas cell setup, in which the molecules are produced via laser ablation of a solid precursor target. Two different kinds of ablation target are used to produce a molecular beam. The first is a pellet of a mixture of CaF2/BaF2. The second is a calcium metal target in addition to sulfurhexafluoride gas, which acts as a fluorine donor. The metal target is found to be the much more stable molecule production method, and the buffer gas cooling setup produces a bright and slow beam of molecules with a flux of around 1011 - 1013sr-1 molecules in the ground state of the laser cooling cycle. The second achievement is a significant improvement of the techniques for laser cooling of the resulting molecular beam. Notably, trapped cold gases of directly laser cooled molecules have not reached the quantum degenerate regime yet, but this milestone is within reach. In our experiment we aim to improve the loading of the magneto optical trap from the laser slowed beam, as this has been the most inefficient step in previous experiments with CaF. Our approach is to collimate the molecular beam through transversal laser cooling on the 𝑋 - 𝐴 transition. Due to the angular momentum structure of the type-II cooling transition, Doppler cooling forces in molecules are typically accompanied by sub Doppler Sisyphus heating forces and vice versa. This has made the collimation of molecular beams difficult in previous experiments, because efficient Doppler cooling over a large velocity range is perturbed by the appearance of sub Doppler heating forces at low transversal velocities. Here, we present a new way to address the hyperfine structure in the molecules using carefully chosen laser sidebands, which overcomes this limitation. The sideband spectrum of the cooling laser consists of one strong sideband with ≈ 80% of the laser power addressing a single hyperfine state and several weaker sidebands which repump population from the other hyperfine states. Depending on the detuning of the cooling laser, the strong sideband generates sub Doppler cooling forces on the 𝑋2Σ+(𝐹 = 2) - 𝐴2Π1/2 (𝐹 = 1) or the 𝑋2Σ+(𝐹 = 1+) - 𝐴2Π1/2 (𝐹 = 0) transition. The measured transversal density profiles of the molecular beam suggest that, for certain detunings of the cooling laser, both mechanisms lead to forces that counteract the molecular motion, leading to the simultaneous appearance of Doppler and sub Doppler cooling. This result is contrary to the conventional tendency of type II systems, where sub Doppler cooling forces are usually opposed by Doppler heating forces. The observed behavior is supported by numerical simulations of the laser cooling forces and molecular trajectories based on the optical Bloch equations. Overall, the results highlight the importance of a well tailored cooling laser sideband structure for molecular laser cooling to control the interplay between both cooling mechanisms. Through the collimation of the molecular motion towards the capture region of a magneto-optical trap, the transversal cooling of the molecular beam with simultaneous Doppler and sub-Doppler cooling forces should enable a more efficient trap loading. The experimental results presented here therefore form the basis for future experiments on laser slowing, magneto optical trapping and evaporative cooling towards Bose Einstein condensation or the loading of large optical tweezer arrays of cold CaF molecules.
Abstract The methods of laser cooling of atoms have long been applied to obtain cold and ultracold atomic gases, including degenerate states and the atomic Bose–Einstein condensate in particular. Until recently the application of laser cooling methods to molecules was assumed to be impossible because of the complex structure of molecular levels and the absence of closed cooling cycles for transitions between the electron levels of molecules in the general case. However, it has recently become clear that laser cooling can be performed for a large class of molecules, including not only the simplest diatomic molecules but also polyatomic molecules. We here present the general principles for identifying suitable molecules and discuss current studies on and further developments in the laser cooling of molecules.
Molecules controlled at the single-quantum-state level offer wide-ranging applications spanning many of the frontiers of modern physics. Within the past decade, simple diatomic molecules have been brought under full quantum control both via assembly from pre-cooled atoms and by direct laser cooling. Polyatomic molecules\footnote{Molecules that contain three or more atoms.} have attracted focus as novel quantum resources providing distinct advantages (and challenges) compared to both atoms and diatomic molecules. For example, nearly all polyatomic molecules have long-lived states that can be fully polarized at low applied electric fields. These and other features generic to polyatomic molecules can be applied to quantum simulation, quantum chemistry, and tests of fundamental physics beyond the Standard Model. While these structural features of polyatomic molecules are highly promising for applications, they complicate the process of bringing molecules under full quantum control. In this thesis, we describe a series of experimental and theoretical advances toward the production of ultracold complex polyatomic molecules. We demonstrate the first laser cooling of the polyatomic radical ytterbium monohydroxide (YbOH), a promising candidate to search for particles and interactions beyond the Standard Model of particle physics. We develop a novel deceleration technique (``Zeeman-Sisyphus deceleration") capable of slowing molecular beams to trappable velocities while scattering fewer than 10 optical photons. This deceleration method is demonstrated using CaOH molecules, a lighter analog of YbOH. In order to determine a viable pathway to full three-dimensional cooling and trapping of YbOH, we develop a spectroscopic technique to measure vibrational branching ratios with relative intensity sensitivity around 1 part in 105, approximately two orders of magnitude beyond the previous state of the art. We also perform the first spectroscopic observations and characterizations of the related molecule ytterbium monomethoxide, YbOCH3, a promising species to probe beyond-the-Standard-Model physics. In addition, we show theoretically that an entire class of asymmetric top molecules can be laser cooled using essentially the same techniques used for much simpler species. Measurements of the vibrational branching ratios for a few prototypical asymmetric to molecules (CaSH and CaNH2) are presented to confirm these predictions.
The cold-molecule field concerns the physics and the applications of molecular systems with translational temperature well below the 1 К range. The possibility of controlling all the motion as well as the internal quantum state of a sample of molecules is a long-term goal that opens the possibility for many new experiments and measurements ranging from fundamental constants to quantum chemistry and quantum computation. Although, direct laser cooling of the translational degree of freedom of molecules is still waiting for further technological or theoretical breakthroughs and ideas, many different techniques have proven to be successful in producing different types of cold as well as ultracold (i.e. T < 1 mK) molecules. In this chapter, we will concentrate on the description of one of these techniques: the photoassociation of laser cooled atoms. We will report on the status of the art of this technique for the case of cesium atoms, describing all the main experimental findings. In particular, we will illustrate the different photoassociation schemes for molecule formation, the detection schemes through photoionization, the molecule trapping in a magnetic or dipolar trap, the vibrational cooling into a single vibrational state and finally the present prospects for rotational cooling.
Photoassociation is the process in which two colliding atoms absorb a photon to form an excited molecule. The development of laser-cooling techniques for producing gases at ultracold (<1mK) temperatures allows photoassociation spectroscopy to be performed with very high spectral resolution. Of particular interest is the investigation of molecular states whose properties can be related, with high precision, to the properties of their constituent atoms with the ``complications'' of chemical binding accounted for by a few parameters. These include bound long-range or purely long-range vibrational states in which two atoms spend most or all of their time at large internuclear separations. Low-energy atomic scattering states also share this characteristic. Photoassociation techniques have made important contributions to the study of all of these. This review describes what is special about photoassociation spectroscopy at ultracold temperatures, how it is performed, and a sampling of results including the determination of scattering lengths, their control via optical Feshbach resonances, precision determinations of atomic lifetimes from molecular spectra, limits on photoassociation rates in a Bose-Einstein condensate, and briefly, production of cold molecules. Discussions are illustrated with examples on alkali-metal atoms as well as other species. Progress in the field is already past the point where this review can be exhaustive, but an introduction is provided on the capabilities of photoassociation spectroscopy and the techniques presently in use.
Quantum degenerate molecular gases are of interest for the unique level of control they offer over chemical interactions and processes. To reach the quantum degenerate regime, these molecular gases must be cooled to ultracold temperatures, typically on the order of 100 nanoKelvins. Unlike atoms, with a few-level system that facilitates cooling, molecules represent a many-level system, which makes these temperatures experimentally difficult to achieve. As a result, experiments have turned to photoassociation and Feshbach resonance as shortcuts to form ultracold molecules from already ultracold atoms. Photoassociation and Feshbach resonance have been utilized to successfully create stable quantum degenerate molecules, but not on a routine basis, and only for a small range of molecular species. The primary focus of this thesis will be to study photoassociation and Feshbach resonance, and investigate possible routes to more efficient long-lived quantum degenerate molecule formation. We will also investigate realistic limiting conditions to open the possibility to more routine molecules, and to molecular species that are currently inaccessible. Overall, we find combined photoassociation and Feshbach resonance are viable schemes for efficiently creating quantum degenerate molecules, under realistic restrictions such as low laser intensity, narrow Feshbach resonance, and strong elastic collisions. As the techniques to create quantum degenerate molecules become more robust and experimentally available, the creation of colder, larger, and more long-lived samples will facilitate study of these molecules, and spur development into new applications.