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 $10^5$, 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, YbOCH$_3$, 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 CaNH$_2$) are presented to confirm these predictions.
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 rich internal structure of polyatomic molecules has inspired a number of theoretical proposals exploring a myriad of unique scientific and engineering frontiers, including quantum simulation and next-generation searches for physics beyond the standard model. Establishing full control over these complex quantum objects is likely necessary to harness their full potential; however, the same rich internal structure that gives rise to the immense scientific potential of polyatomic molecules also makes manipulating them a daunting task. In the past decade there has been considerable progress in the production, cooling, and control of diatomic species using direct laser cooling and magneto-optical trapping. This dissertation focuses on extending direct laser cooling and trapping to polyatomic molecules. Direct laser cooling of triatomic radical calcium monohydroxide (CaOH) is demonstrated. This molecules is a prototypical example of a broad class of polyatomic molecules that includes symmetric and asymmetric tops. Transverse magneto-optical trapping is demonstrated, establishing the ability to scatter an unprecedented number of photons in a polyatomic species. An understanding of previously unappreciated intricacies of molecular structure is developed, that explains observations of novel vibrational decay pathways. High resolution spectroscopy of hybrid vibrational modes is performed. A laser cooling scheme is constructed that will support future efforts to use the full range of laser cooling and high-fidelity detection techniques required to implement an optical tweezer array of polyatomic molecules. Our experimental efforts demonstrate the feasibility of direct laser cooling applied to CaOH, up ending long-standing assumptions of the inextricable complexity of polyatomic molecules.
Polyatomic molecules contain diverse structures – including rotational and vibrational degrees of freedom, nuclear and electronic spins, and electric dipole moments – that make them promising for a range of quantum science applications. These include quantum information science, quantum simulation, studies of ultracold collisions and ultracold chemistry, and precision searches for physics beyond the Standard Model. However, maximizing the potential of polyatomic molecules for these applications requires them to be cooled to ultracold temperatures ( mK), trapped in three dimensions, and controlled at the single quantum state level. Significant progress has been made with diatomic molecules over the last fifteen years, but the increased complexity of polyatomic species (defined as molecules containing more than two atoms) makes them more challenging to control at the same level. In this thesis, we describe our work bringing a linear triatomic molecule, calcium monohydroxide (CaOH), into the quantum regime. We demonstrate laser cooling of CaOH molecules to microkelvin temperatures, confinement in a magneto-optical trap (MOT), and loading of conservative optical dipole traps and optical tweezer arrays. We characterize the lifetime of low-lying vibrational states of CaOH in optical traps, including the vibrational bending mode, whose parity-doublet states are a key resource for many applications. Next, we develop techniques for preparing CaOH molecules in a single internal quantum state and for coherently manipulating the internal state with microwave and radio-frequency fields. We also show that we can nondestructively and state-selectively detect trapped CaOH molecules, including single molecules in optical tweezers. We demonstrate the applicability of these tools to applications including precision measurements, quantum information science, and ultracold collisions. We establish a method for future CP-violating physics searches with optically trapped polyatomic molecules, by identifying states that are sensitive to the electron electric dipole moment (eEDM) and showing that these states have long coherence times in CaOH. We identify potential qubit states in the CaOH bending mode and show that they can be coherently controlled at the single-molecule level in an optical tweezer array. Finally, we observe and characterize single quantum-state-controlled collisions between ultracold CaOH molecules, and identify states in the bending mode that could potentially be used for evaporative cooling to quantum degeneracy. Compared to linear triatomic molecules, nonlinear molecules contain even more structures that can be harnessed for quantum science applications, at the cost of making them even more challenging to cool and control. Towards this goal, in this thesis we describe work demonstrating 1D laser cooling of a beam of CaOCH3, a symmetric top molecule. This contributes to a growing body of evidence that complex polyatomic molecules could soon be cooled, trapped, and controlled at ultracold temperatures.
Ultracold molecules are a promising platform for a wide range of applications in quantum science, including searches for new particles (beyond the Standard Model), quantum computing and simulation, and studies of ultracold collisions and chemistry. Over the last decade, tremendous progress has been made in developing techniques to trap diatomic molecules (molecules containing only two atoms) and cool them to ultracold temperatures using laser cooling. Polyatomic molecules (molecules containing more than two atoms) provide new, unique scientific opportunities not afforded by their diatomic counterparts and represent the next frontier in laser cooling and quantum science with molecules. In this thesis, we present our work on extending laser cooling and quantum control to polyatomic molecules. We describe our demonstration of laser cooling and the creation of a magneto-optical trap (MOT) of a polyatomic molecule, calcium monohydroxide (CaOH). We further demonstrate loading of the trapped molecules into an optical dipole trap (ODT) and loading of individual CaOH molecules into the conservative potential an optical tweezer array. We also describe our realization of a new type of MOT developed for molecules, a "conveyor belt MOT", which provides increased compression compared to traditional molecular MOTs and was discovered using numerical simulations of the CaOH MOT that were developed as part of this thesis. The increased MOT density and ODT loading afforded by the conveyor belt MOT provides the density required to perform studies of collisions between ultracold CaOH molecules. We also describe our work on the laser cooling the symmetric top molecule CaOCH₃, opening the possibility for 3-D laser cooling of even larger, more complex molecules into the ultracold regime. With the ability to laser cool and trap CaOH molecules, our most recent work has focused on developing tools for quantum control and on initial explorations of some of the new features afforded by polyatomic molecules. We describe a novel protocol established to perform a measurement of the electron's electric dipole moment ("eEDM"). Looking towards quantum information processing with polyatomic molecules, we create a new type of qubit using parity-doublet states in the bending mode of CaOH and characterize its coherence properties. Finally, we provide a brief outlook towards the future of laser cooling of polyatomic molecules for quantum science and provide a few suggestions for new directions opened up by the work presented in this thesis.
Extending AMO techniques of motional control to heavy polyatomic molecules opens new possibilities for precision measurements of fundamental physics. Though various laser-cooling and deceleration techniques have been applied to diatomic molecules throughout the last decade, their application to more complex molecules has heretofore been focused on light species, leaving generalizability to heavy species an open question. To investigate the high-mass frontier, we here study how to extend motional control to heavy-atom-containing polyatomic molecules. First, we discuss Zeeman-Sisyphus deceleration of YbOH, which can be used to decelerate species capable of scattering only ~10s of photons. Then, we discuss radiative slowing and magneto-optical trapping of SrOH, techniques only extendable to species capable of scattering ∼104 photons. The last work focuses on spectroscopy of nonlinear molecules to assess the viability of extending techniques of motional control to more complex species. We find a dependence of both rotational and vibrational control on symmetry group, and identify a next-generation candidate for laser cooling. We end with a overview tying these projects together, and assessing the future of motional control along mass and complexity axes, including brief suggestions of how complementary methods to those studied here can further expand into the frontiers of molecular control.
Polyatomic molecules, while ubiquitous in nature, were generally perceived as too complicated and "unruly" for the majority of quantum physics experiments. However, recent theoretical analyses have pinpointed the multiple advantages of using complex molecules for diverse applications such as the creation of a universal quantum computer, quantum simulation of non-trivial many-body states, and tests of fundamental physical laws. Throughout my dissertation research I focused on extending experimental techniques from atomic physics to complex molecules. The goal of my work was to not only demonstrate new ways to control molecules, but also develop a novel experimental platform for quantum science - complex polyatomic molecules - and provide tools for physicists to conquer new frontiers in physics and chemistry.\nThe main theme of this thesis is the use of laser radiation to control internal and external degrees of freedom for the triatomic radical strontium monohydroxide (SrOH). The research achievements presented here can be primarily divided into the following areas:\ni) out-of-equilibrium studies of vibrationally inelastic collisions at cryogenic temperatures,\nii) demonstration of the radiation pressure force and the direct laser cooling of polyatomic molecules, and\niii) the development of concepts for laser cooling of molecules with six and more atoms.\nFor the collisional studies, off-diagonal optical pumping was used to populate excited Sr-O stretching state and the ratio of elastic to vibrational quenching collisions was determined to be ~700. In the laser cooling work, using only laser light, the transverse temperature of the cryogenic buffer-gas beam of SrOH was reduced from 50 mK to below 1 mK, leading to an order of magnitude increase in phase space density of the molecular beam. Additionally, the prospects of using a coherent bichromatic force for optical deceleration of polyatomics were analyzed and experimentally characterized with the transverse deflection of the SrOH beam. Our experimental results with SrOH and theoretical analysis of more complex strontium alkoxides not only open a wide range of future directions for laser manipulation and trapping of polyatomic molecules but also help overturn long held assumptions about the difficulties of performing "traditional" atomic physics experiments with complex molecules.
Abstract Precision measurements in molecules have advanced rapidly in recent years through developments in techniques to cool, trap, and control. The complexity of molecules makes them a challenge to study, but also offers opportunities for enhanced sensitivity to many interesting effects. Polyatomic molecules offer additional complexity compared to diatomic molecules, yet are still ‘simple’ enough to be laser-cooled and controlled. While laser cooling molecules is still a research frontier itself, there are many proposed and ongoing experiments seeking to combine the advanced control enabled by ultracold temperatures with the intrinsic sensitivity of molecules. In this perspective, we discuss some applications where laser-cooled polyatomic molecules may offer advantages for precision measurements of fundamental physics, both within and beyond the Standard Model.