This thesis comprises two topics in the field of the ultracold atomic and molecular physics, both involving formation of ultracold 85Rb 2 by photoassociation (PA). Typically, these ground-state molecules are formed mainly in the very highest vibrational levels, rather than the low-v levels that will be required for most future investigations of ultracold molecular physics and chemistry. The first topic of my research is a method for circumventing this problem: resonant enhancement (RE) of photoassociative ground-state molecule production. The key idea of RE is to photoassociate pairs of colliding atoms into an excited state that has a bimodal vibrational probability distribution, with one peak at long range to enhance the photoassociation rate and another at shorter range to enhance radiative decay into deeply bound levels of the ground state. This can be arranged thanks to the strong spin-orbit perturbative interaction between the two 0+u states converging to two different asymptotes, (5s + 5p1/2) and (5s + 5 p3/2). This method enhances ground-state molecule formation in the region well below the dissociation limit. The experimental work described here was done at the University of Connecticut in collaboration with C. P. Koch at the Institut für Theoretische Physik, Freie Universität Berlin, Germany, who performed the theoretical analysis [1].^ The second part of my thesis is the investigation of ultracold molecules in an optical dipole trap. We have constructed a quasi-electrostratic optical trap (QUEST) for 85Rb using a focused CO2 laser [2]. This provides a very high density of ultracold atoms, up to 10 12 cm-3, providing much higher photoassociation rates. It also keeps the molecules trapped once they have formed. The QUEST provides an ample trapping lifetime for both trapped atoms and molecules, yielding about 4-5×106 atoms and about 9×105 high-v molecules. The long lifetime of the trapped molecules and atoms, combined with their high density, allows us to study interactions such as atom-molecule or molecule-molecule collisions in the ultracold regime. A preliminary experiment on Rb2 molecular decay is described. ^
This thesis comprises two topics in the field of the ultracold atomic and molecular physics, both involving formation of ultracold 85Rb 2 by photoassociation (PA). Typically, these ground-state molecules are formed mainly in the very highest vibrational levels, rather than the low-v levels that will be required for most future investigations of ultracold molecular physics and chemistry. The first topic of my research is a method for circumventing this problem: resonant enhancement (RE) of photoassociative ground-state molecule production. The key idea of RE is to photoassociate pairs of colliding atoms into an excited state that has a bimodal vibrational probability distribution, with one peak at long range to enhance the photoassociation rate and another at shorter range to enhance radiative decay into deeply bound levels of the ground state. This can be arranged thanks to the strong spin-orbit perturbative interaction between the two 0+u states converging to two different asymptotes, (5s + 5p1/2) and (5s + 5 p3/2). This method enhances ground-state molecule formation in the region well below the dissociation limit. The experimental work described here was done at the University of Connecticut in collaboration with C. P. Koch at the Institut für Theoretische Physik, Freie Universität Berlin, Germany, who performed the theoretical analysis [1].^ The second part of my thesis is the investigation of ultracold molecules in an optical dipole trap. We have constructed a quasi-electrostratic optical trap (QUEST) for 85Rb using a focused CO2 laser [2]. This provides a very high density of ultracold atoms, up to 10 12 cm-3, providing much higher photoassociation rates. It also keeps the molecules trapped once they have formed. The QUEST provides an ample trapping lifetime for both trapped atoms and molecules, yielding about 4-5×106 atoms and about 9×105 high-v molecules. The long lifetime of the trapped molecules and atoms, combined with their high density, allows us to study interactions such as atom-molecule or molecule-molecule collisions in the ultracold regime. A preliminary experiment on Rb2 molecular decay is described. ^
We have studied the effect of resonant electronic-state coupling on the formation of ultracold ground-state 85Rb2. Ultracold Rb2 molecules are formed by photoassociation (PA) to a coupled pair of 0u+ states, 0u+(P1∕2) and 0u+(P3∕2), in the region below the 5S+5P1∕2 limit. Subsequent radiative decay produces high vibrational levels of the ground state, $X\phantom{\rule{0.2em}{0ex}}^{1}\ensuremath{\Sigma}_{g}^{+}$. The population distribution of these X-state vibrational levels is monitored by resonance-enhanced two-photon ionization through the $2\phantom{\rule{0.2em}{0ex}}^{1}\ensuremath{\Sigma}_{u}^{+}$ state. We find that the populations of vibrational levels ${v}^{\ensuremath{''}}=112--116$ are far larger than can be accounted for by the Franck-Condon factors for ${0}_{u}^{+}({P}_{1∕2})\ensuremath{\rightarrow}X\phantom{\rule{0.2em}{0ex}}^{1}\ensuremath{\Sigma}_{g}^{+}$ transitions with the 0u+(P1∕2) state treated as a single channel. Further, the ground-state molecule population exhibits oscillatory behavior as the PA laser is tuned through a succession of 0u+ state vibrational levels. Both of these effects are explained by a calculation of transition amplitudes that includes the resonant character of the spin-orbit coupling of the two 0u+ states. The resulting enhancement of more deeply bound ground-state molecule formation will be useful for future experiments on ultracold molecules.
In the first part of this dissertation we develop and successfully demonstrate two methods, based on photoassociation of ultracold potassium atoms, for producing ultracold K2 molecules, with sub mK temperatures, in deeply bound vibrational levels of the ground XS+g 1 state. The principal objective has been to develop an “ultracold molecule factory” that can be used to support experiments on spectroscopy, collisions, and chemistry of ultracold molecules. ^ In the first experiment the ground-state molecules are produced by the radiative decay of excited, n≅191 AS+u 1 state molecules, photoassociated from ultracold potassium atoms in a vapor-cell MOT. The decay is primarily into the vibrational continuum, but a small fraction decays into bound levels of the X state near n = 36. The experimentally observed molecule production rate is about 103 per second. ^ In our second experiment, we use two-step laser excitation to effect an “R-transfer” from long-range to intermediate internuclear separations, greatly increasing the efficiency for radiative production of low- n molecules in the X state. Molecules are formed in the Pg1 state by photoassociation, then excited by a second laser to the 51Pu or 61Pu Rydberg states, in selected vibrational levels from n = 13–18. Finally, radiative decay produces very large numbers of X state molecules with n≅25 and significant numbers of molecules in very low vibrational levels, including n = 0. We have observed production rates up to about 105 molecules/second per vibrational level. ^ In both experiments the ground-state molecules are detected with a sensitive and selective resonant two-color photoionization with nanosecond pulses. ^ In the second part of this dissertation we demonstrate a novel method for high sensitivity absorption measurements, that combines a phase modulated, high-resolution pulsed laser with an actively stabilized optical cavity to achieve a sensitivity of ∼10−9 per cm. This is comparable to the best existing methods for pulsed absorption measurements, but unlike most other methods, it can also be readily extended to the UV region and to Doppler-free spectroscopy. ^
Heteronuclear polar molecules have recently attracted enormous attention owing to their ground state having a large electric dipole moment. The long range anisotropic dipole-dipole interaction in such systems is the basis for a variety of applications including quantum computing, precision measurements, ultracold chemistry and quantum simulations. Heteronuclear bi-alkali molecules, only a small subset of polar molecules, have received special attention mainly because the constituent alkali atoms are easy to laser cool and can be relatively easily associated to form molecules at ultracold temperatures. Our choice, the LiRb molecule, is motivated by the relatively high dipole moment (4.1 Debye) of the LiRb molecule in its rovibronic ground state. In this thesis, we study the LiRb molecule using laser spectroscopy and report, for the first time, the production of ultracold LiRb molecules by photoassociation (PA). The LiRb molecule is the least studied among all bi-alkali molecules and the first spectroscopic measurements on hot vapor phase LiRb molecules were reported only in 2011. We describe these measurements and their significance in chapter 2, after a brief introduction to the field of ultracold polar molecules in chapter 1. In chapter 3, we discuss our apparatus for simultaneous cooling and trapping of Li and Rb atoms in a dual-species magneto-optical trap (MOT) and report the measurement of interspecies collision-induced losses. In chapter 4, we describe the production of ultracold LiRb molecules in excited electronic states by photoassociation (PA). We report the measurements of the C6 coefficients for the Li (2s 2S1/2) + Rb (5p 2P1/2) and the Li (2s 2S1/2) + Rb (5p 2P3/2) asymptotes. We find a molecule formation rate (PLiRb) as high as 3.5x107 s-1 and a PA rate coefficient (KPA) as high as 1.3x10-10 cm3/s, the highest among heteronuclear bi-alkali molecules. In chapter 5, we discuss results on two-photon PA and we conclude, in chapter 6, with a road roadmap of future experiments for the production and detection of ultracold LiRb molecules in their rovibronic ground state.
In this thesis properties of ultracold alkali dimers are studied both theoretically and experimentally. In the first, theoretical, part, the prospects for the formation of ultracold LiCs dimers in deeply bound vibrational levels using photoassociation (PA) are investigated. Furthermore a previous systematic investigation of the structure of all alkali dimers is extended by the ab initio calculation of static dipole polarizabilities. An extensive comparison with other published results supports the reliability of the chosen method. Based on these results an experimental scheme for the creation of an sample of oriented ultracold dipolar molecules is developed. In the second, experimental part the formation of LiCs ground state molecules by PA is investigated. PA spectroscopy is used to improve the accuracy of the potential energy curve for the B1P and the value of the dissociation energy of the X1S+ state significantly. The rovibrational distribution of ground state molecules is probed in a combination of resonance-enhanced multi-photon ionization and depletion spectroscopy. A simple scheme is found to form ultracold polar LiCs molecules in the absolute ground state X1S+,v''=0,J''=0. In a quasi-electrostatic trap created by a CO2 laser, LiCs molecules are formed and stored. A lifetime of 24(3)s, limited by collisions with background gas, is observed and rate coefficients for inelastic collisions between LiCs in high vibrational states and Cs atoms are determined. The long storage time facilitates the observation of radiative decay of polar molecules towards lower vibrational levels.
We form ultracold ground-state Rb 2 molecules by photoassociating pairs of atoms in a magneto-optical trap into the 0 u + state, which decays radiatively into high vibrational levels of the X 1 Σ g + state. Sensitive and vibrationally state-selective detection is achieved by means of resonantly-enhanced two-photon ionization with a pulsed laser. Frequency scans of the detection laser reveal a long vibrational progression to a previously unobserved electronic excited state, which we identify as the 2 1 Σ u + state. Most of its vibrational spectrum is in excellent agreement with predictions based on ab initio potentials, although the lowest vibrational levels exhibit strong perturbative mixing with the triplet 2 3 Π u state. The detection method reported here, with minor variations, should be effective for the entire potential well of the X state. In this work no transitions are observed from vibrational levels above v = 118, but this turns out to be a limitation not of the detection method but rather of the photoassociative formation scheme, due to re-excitation of the highest- v levels by the same photoassociation laser that produces them.
Utilizing single-photon photoassociation, we have achieved ultracold rubidium molecules with a high number density that provides a new efficient approach toward molecular quantum degeneracy. A new detection mechanism for ultracold molecules utilizing inelastic atom–molecule collision is demonstrated. The resonant coupling effect on the formation of the X 1 Σ + g ground state 85 Rb 2 allows for a sufficient number of more deeply bound ultracold molecules, which induced an additional trap loss and heating of the co-existing atoms owing to the inelastic atom–molecule collision. Therefore, after the photoassociation process, the ultracold molecules can be investigated using the absorption image of the ultracold rubidium atoms mixed with the molecules in a crossed optical dipole trap. The existence of the ultracold molecules was then verified, and the amount of accumulated molecules was measured. This method detects the final produced ultracold molecules, and hence is distinct from the conventional trap loss experiment, which is used to study the association resonance. It is composed of measurements of the time evolution of an atomic cloud and a decay model, by which the number density of the ultracold 85 Rb 2 molecules in the optical trap was estimated to be >5.2 × 10 11 cm −3 .