Cold and ultracold molecules are highly desirable for a diverse range of applications in physics and chemistry such as precision measurements, tests of fundamental physics, quantum simulation and information processing, quantum chemistry, and the physics of strongly correlated quantum matter. Laser cooling is usually infeasible in molecules because their rotational and vibrational transitions make is difficult to come up with a closed scattering cycle. Recently, a narrow range of diatomic molecules, one of which is CaF, has been shown to possess a convenient electronic structure and a highly-diagonal Franck-Condon matrix and thus be amenable to laser cooling. This thesis describes experiments on laser cooling of CaF radicals produced in a supersonic source. We first investigate the increased fluorescence when multi-frequency resonant light excites the molecules from the four hyperfine levels of the ground X²∑+(N = 1, v = 0) state to the first excited A²π½ (J’ = 1=2; v’ = 0) state. The number of photons scattered per molecule increases significantly from one or two in the single frequency case to more than 50 before the molecules get pumped into the X²∑+(N = 1; v = 1) state. We demonstrate laser cooling and slowing of CaF using counter-propagating laser light which causes the molecules to scatter more than a thousand photons on the X (N = 1, v = 0, 1) <->A (J’ = 1=2; v’ = 0) transition. The effect of the laser cooling is to slow a group of molecules from 600 ms-1 to about 580 ms-1 and to narrow their velocity distribution from an initial temperature of 3 K down to 300 mK. In addition, chirping the frequency of the cooling light to keep it on resonance with the decelerating molecules doubles the deceleration and further compresses the velocity distribution. The effect of the laser cooling is limited by the optical pumping of molecules in the X (N = 1, v = 2) state.
Cold and ultracold molecules are highly desirable for a diverse range of applications in physics and chemistry such as precision measurements, tests of fundamental physics, quantum simulation and information processing, quantum chemistry, and the physics of strongly correlated quantum matter. Laser cooling is usually infeasible in molecules because their rotational and vibrational transitions make is difficult to come up with a closed scattering cycle. Recently, a narrow range of diatomic molecules, one of which is CaF, has been shown to possess a convenient electronic structure and a highly-diagonal Franck-Condon matrix and thus be amenable to laser cooling. This thesis describes experiments on laser cooling of CaF radicals produced in a supersonic source. We first investigate the increased fluorescence when multi-frequency resonant light excites the molecules from the four hyperfine levels of the ground X²∑+(N = 1, v = 0) state to the first excited A²π½ (J’ = 1=2; v’ = 0) state. The number of photons scattered per molecule increases significantly from one or two in the single frequency case to more than 50 before the molecules get pumped into the X²∑+(N = 1; v = 1) state. We demonstrate laser cooling and slowing of CaF using counter-propagating laser light which causes the molecules to scatter more than a thousand photons on the X (N = 1, v = 0, 1) <->A (J’ = 1=2; v’ = 0) transition. The effect of the laser cooling is to slow a group of molecules from 600 ms-1 to about 580 ms-1 and to narrow their velocity distribution from an initial temperature of 3 K down to 300 mK. In addition, chirping the frequency of the cooling light to keep it on resonance with the decelerating molecules doubles the deceleration and further compresses the velocity distribution. The effect of the laser cooling is limited by the optical pumping of molecules in the X (N = 1, v = 2) state.
We demonstrate slowing and longitudinal cooling of a supersonic beam of CaF molecules using counterpropagating laser light resonant with a closed rotational and almost-closed vibrational transition. A group of molecules are decelerated by about 20 m/s by applying light of a fixed frequency for 1.8 ms. Their velocity spread is reduced, corresponding to a final temperature of about 300 mK. The velocity is further reduced by chirping the frequency of the light to keep it in resonance as the molecules slow down.
From studies of fundamental physics to quantum technologies the production of ultracold molecules will have a huge impact across a range of applications. For many years laser cooling, which became an invaluable tool in cold atomic physics, was deemed to be too impractical for application to molecules. Nevertheless, laser cooling has now been demonstrated for a few molecular species. Using a frequency-chirped laser slowing technique, the velocity distribution of a pulse of CaF molecules is compressed and slowed from 180 m/s to about 10 m/s. These slow molecules are then captured in a magneto-optical trap. I present measurements that show how the number of molecules, the photon scattering rate, the oscillation frequency, damping constant, temperature, cloud size and lifetime depend on the key parameters of the magneto-optical trap, especially the intensity and detuning of the main cooling laser. The trap contains up to 2*10^4 molecules, the maximum photon scattering rate is 2.5*10^6 s-1 per molecule, the maximum oscillation frequency is 100 Hz, the maximum damping constant is 500 s^-1, and the minimum rms radius of the trapped cloud is 1.5 mm. A minimum temperature of 730 microkelvin is obtained by ramping down the laser intensity to lower values. To reach lower temperatures, the cloud is loaded into a blue-detuned optical molasses, which cools the molecules to 55 microkelvin, well below the Doppler-limiting temperature. I characterise the cooling process and suggest the sub-Doppler mechanisms responsible. These ultracold molecules are the optically pumped into a single quantum state, and coherently transferred between selected hyperfine components of the ground and first-excited rotational states. Finally, the ultracold, state-selected molecules are loaded into a magnetic trap that has a lifetime of about 1 s.
Ultracold molecules can be used for a diverse set of exciting applications including controlled quantum chemistry, probes of physics beyond the standard model, simulation of many-body quantum systems and quantum information processing. However their rich internal structure makes the required control of their motional and internal states difficult. In the last decade, the field has made rapid progress on developing techniques for producing, cooling and trapping molecules and, whilst challenges remain, many of these applications are now being realised. This thesis presents my work on laser cooling and coherent control of calcium monofluoride (CaF) molecules. We load molecules into a three-dimensional magneto-optical trap (MOT), the first such trap for CaF and the second for any molecule. The MOT contains around 2×10⁴ molecules with an initial temperature of 12 mK. Lowering the laser intensity brings the temperature of the MOT down to 960 μK. To further cool the molecules we load them into a blue-detuned optical molasses, cooling them to 5.4(7) μK. This temperature is ~40 times below the Doppler limit and corresponds to a typical molecule moving at only a few times the single-photon recoil velocity. We optically pump the molecules into a single Zeeman sub-level and coherently transfer them between rotational states using microwave radiation. We load the molecules into a magnetic trap where they remain confined for about 5 s, the lifetime being limited by vibrational excitation due to room-temperature blackbody radiation. We show how to prepare the trapped molecules in a coherent superposition of two rotational states, and how to maintain this coherence for long periods, up to 6.4(8) ms. Detailed simulations of the remaining decoherence mechanisms suggest that it is possible to extend this to more than a second by compressing the sample to a smaller size, and using a magnetic trap geometry where the direction of the field is nearly uniform across the trapping volume. Finally we explore theoretically how Raman sideband cooling can be applied to molecules in optical tweezer traps, potentially providing a route to full quantum control.
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.
Laser cooling and trapping are central to modern atomic physics. It has been roughly three decades since laser cooling techniques produced ultracold atoms, leading to rapid advances in a vast array of fields and a number of Nobel prizes. Prior to the work presented in this thesis, laser cooling had not yet been extended to molecules because of their complex internal structure. However, this complexity makes molecules potentially useful for a wide range of applications. The first direct laser cooling of a molecule and further results we present here provide a new route to ultracold temperatures for molecules. In particular, these methods bridge the gap between ultracold temperatures and the approximately 1 kelvin temperatures attainable with directly cooled molecules (e.g. with cryogenic buffer gas cooling or decelerated supersonic beams). Using the carefully chosen molecule strontium monofluoride (SrF), decays to unwanted vibrational states are suppressed. Driving a transition with rotational quantum number R=1 to an excited state with R'=0 eliminates decays to unwanted rotational states. The dark ground-state Zeeman sublevels present in this specific scheme are remixed via a static magnetic field. Using three lasers for this scheme, a given molecule should undergo an average of approximately 100,000 photon absorption/emission cycles before being lost via unwanted decays. This number of cycles should be sufficient to load a magneto-optical trap (MOT) of molecules. In this thesis, we demonstrate transverse cooling of an SrF beam, in both Doppler and a Sisyphus-type cooling regimes. We also realize longitudinal slowing of an SrF beam. Finally, we detail current progress towards trapping SrF in a MOT. Ultimately, this technique should enable the production of large samples of molecules at ultracold temperatures for molecules chemically distinct from competing methods.
Diatomic molecules are considered good candidates for the study of strongly correlated systems and precision measurement searches due to their combination of complex internal states and strong long-range interactions. Cooling molecules down to ultracold temperatures is often a necessary step for fully utilizing the power of the molecule. This requires a trap for molecules and the ability to cool molecules to the mK regime and below. A magneto-optical trap (MOT) is a good tool for achieving mK temperatures. However, extra care is needed for molecules to form the necessary quasi-closed cycling transitions due to molecule's complicated energy structure. In our work with CaF, we use two repump lasers to block vibrational leakage and selection rules for the rotational degree of freedom to achieve about 10^{5} photon cycles.\n\n\n\nThe two-stage buffer gas beam source is a general method to generate a cold and slow beam of molecules with a forward velocity of about 50 m/s. The compatibility of the buffer-gas source with a MOT is studied and we confirm that such beams can be nicely compatible with MOTs using various atomic species. \n\n\n\nIn order to load molecules into a MOT from even such a slow beam, additional slowing is required due to the low capture velocity of a molecular MOT (< 10 m/s). We apply a frequency-broadened “white-light” slowing on CaF from a two-stage source, demonstrating slowing of CaF below 10 m/s. An AC MOT, which provides active remixing of dark substates, is also developed and Li atoms are slowed and trapped. These are crucial ingredients for co-trapping CaF molecules and Li atoms and study their collisional properties, which would lead to sympathetic cooling of molecules down to ultracold temperatures. \n\n\n\nThe achievement of slowing and development of this system allowed for the detailed study of the CaF laser cooling system, as well as physical processes involved with AC MOTs and the proposed MOT for CaF. Crucial knowledge of this archetypal system provides significant progress toward manipulation and control of molecules similar to what has been achieved with atoms and what is necessary for searches for new physics with ultracold molecules.