Carbon monoxide molecules in their electronic, vibrational, and rotational ground state are highly attractive for trapping experiments. The optical or ac electric traps that can be envisioned for these molecules will be very shallow, however, with depths in the sub-milliKelvin range. Here, we outline that the required samples of translationally cold CO (X(1)Σ(+), v'' = 0, N'' = 0) molecules can be produced after Stark deceleration of a beam of laser-prepared metastable CO (a(3)Π(1)) molecules followed by optical transfer of the metastable species to the ground state via perturbed levels in the A(1)Π state. The optical transfer scheme is experimentally demonstrated and the radiative lifetimes and the electric dipole moments of the intermediate levels are determined.
Carbon monoxide molecules in their electronic, vibrational, and rotational ground state are highly attractive for trapping experiments. The optical or ac electric traps that can be envisioned for these molecules will be very shallow, however, with depths in the sub-milliKelvin range. Here, we outline that the required samples of translationally cold CO (X(1)Σ(+), v'' = 0, N'' = 0) molecules can be produced after Stark deceleration of a beam of laser-prepared metastable CO (a(3)Π(1)) molecules followed by optical transfer of the metastable species to the ground state via perturbed levels in the A(1)Π state. The optical transfer scheme is experimentally demonstrated and the radiative lifetimes and the electric dipole moments of the intermediate levels are determined.
Ultracold matter offers a unique capability to reach the best high-precision spectroscopy measurements and leads to exciting perspectives in many different areas of science and technology. Molecules, thanks to their complex spectra, couple with a broader range of photons compared to atoms, so they are extremely attractive for fundamental science or to design new quantum technologies. However, to date, only a few molecular species have been brought to temperatures of the order of the microkelvin. This was done by laser cooling, a process that has been demonstrated only for species featuring an unpaired electron that does not participate to the chemical bond. \n \nA different approach, which is indifferent to the molecule electronic structure and thus potentially universal, is sympathetic cooling, where neutral molecules are cooled in a bath of ultracold atoms. However, inelastic collisions between molecules and the coolant is a major obstacle that has hindered the advances of this method thus far. Trapping the molecules in their absolute ground state would circumvent this problem or at least greatly simplify it. In this thesis we simulate the feasibility of an experiment in which metastable CO molecules are first slowed down to a few m/s with a microstructured Stark decelerator, then they are stopped by a strong DC electrical barrier and finally they are transferred irreversibly to their absolute ground state and captured in an optical trap. \nUnfortunately, the results of the simulations indicate that the total number of molecules that can be accumulated in the optical trap is rather low, far behind the observation threshold. Therefore, we concluded that other approaches to produce ultracold molecules must to be searched.
Inspired by the spectacular successes in the field of cold atoms, there is currently great interest in cold molecules. Cooling molecules is useful for various fundamental physics studies and gives access to an exotic regime in chemistry where the wave property of the molecules becomes important. Although cooling molecules has turned out to be considerably more difficult than cooling atoms, a number of methods to produce samples of cold molecules have been demonstrated over the last few years. This paper aims to review the application of cold molecules and the methods to produce them. Emphasis is put on the deceleration of polar molecules using time-varying electric fields. The operation principle of the array of electrodes that is used to decelerate polar molecules is described in analogy with, and using terminology from, charged-particle accelerators. It is shown that, by applying an appropriately timed high voltage burst, molecules can be decelerated while the phase-space density, i.e. the number of molecules per position-velocity interval, remains constant. In this way the high density and low temperature in the moving frame of a pulsed molecular beam can be transferred to the laboratory frame. Experiments on metastable CO in states that are either repelled by or attracted to high electric fields are presented. Loading of slow molecules into traps and storage rings is discussed.
A lithographically-etched chip containing 1254 microscopic electrodes at a\ncenter-to-center spacing of 40 micron is used to produce an array of electric\nfield strength minima 25 micron above the surface with a spacing between\nneighboring minima of 120 micron. These minima are produced by applying a\nseries of six potentials to the electrodes. For polar molecules in low field\nseeking states, the electric field minima are potential energy minima and thus\nact as traps. By varying the potentials in a controlled manner, the field\nminima can be translated with respect to the electrodes at a constant distance\nfrom the surface. Experiments were performed with CO in the metastable a\n3-Pi-1, v = 0, J = 1 state, which has a strong, linear Stark shift with low\nfield seeking components, a 6 eV internal energy that enables easy detection\nthrough an Auger process, and a radiative lifetime of 2.6 ms, which is long\nenough for the experiments here. CO molecules in a pulsed molecular beam are\ndirectly excited to the metastable state with a 5 ns laser pulse. The\nmetastable CO molecules pass through a skimmer and arrive to the chip\ntraveling parallel to the surface and perpendicular to the electrodes. While\nabove the chip, the molecules are manipulated by the electric fields and\nsubsequently ejected from the other side toward the detector. Metastable 12-CO\nmolecules have been guided over the chip at constant velocities and\ndecelerated. As the final velocity decreases (i.e. the deceleration\nincreases), the decelerated molecules arrive at the detector successively\nlater, and the number of decelerated molecules reaching the detector also\ndecreases. While this effect is expected, the fraction of molecules lost is\nmuch greater than trajectory simulations predict. Most of this excess loss at\nhigher decelerations results from non-adiabatic transitions to untrapped\nstates. At zero electric field, the low field seeking level of the a 3-Pi-1, v\n= 0, J = 1 state of 12-C-16-O is exactly degenerate with a level that is only\nweakly affected by the fields. As the molecules pass near the zero field\nregion at the center of a microtrap, they can transition to this level, after\nwhich they are lost from the trap. One way to avoid this loss channel is to\nuse 13-C-16-O instead of 12-C-16-O, which results in a breaking of this\ndegeneracy by 50 MHz due to hyperfine structure. Because of this splitting,\nensembles of metastable 13-C-16-O molecules can and have been decelerated to\nzero velocity above the chip and held for variable durations ranging from 0 ms\nto 2.5 ms. It is observed that fewer molecules are detected after longer\ntrapping times on the chip, but the rate of this loss is consistent with the\n2.6 ms radiative lifetime of the metastable CO molecules. Further experiments\ndemonstrate that the Zeeman splitting due to an external magnetic field\nperpendicular to the electric field is a valid and more general way to prevent\nnon-adiabatic losses in 12-CO.
We propose a general scheme for sympathetic cooling of molecules to microK temperatures on a timescale of seconds. Experimental parameters have been estimated from theory, which indicate the viability of the scheme. This method, which is particularly suited to optical Stark deceleration, utilises ultracold, laser cooled metastable rare gas atoms quenched to their ground state as collision partners to co-trapped molecular species within a deep optical trap (150 mK). We also describe the measurement of the role of laser-induced molecular alignment on the dipole force in optical Stark deceleration and outline progress towards the realisation of chirped optical Stark deceleration for producing slow molecular beams with mK energy spreads.
This thesis describes the design and construction of a novel molecule-surface scattering apparatus. The setup combines a Stark decelerator with a state-of- the-art surface scattering chamber, and allows background-gas free scattering of packets of velocity-controlled polar molecules in selected quantum states from well-defined surfaces with unprecedented energy resolution. Results for scattering of CO (a3Π) in different vibrational quantum states from a clean Au(111) surface are presented. CO is co-expanded with Xe or Ar to yield a supersonic molecular beam which produces fast, internally cold molecules. Excitation of CO to the long-lived electronically excited a3Π1 state makes it accessible to manipulation with electric fields due to the state’s large dipole moment. The complete removal of both carrier gas and remaining ground- state CO is achieved by focusing and deflecting the metastable CO with a switched electrostatic hexapole state selector. The 131-stage Stark decelerator is used to tune the velocity of a part of the metastable CO pulse, with an initial velocity of 360 m/s, in the range from (512 ± 4) m/s – (50 ± 4) m/s, corresponding to an incident translational energy between (307 ± 5) cm-1 and (3.0 ± 0.5) cm-1, respectively.This range can be extended up to (1300 ± 25) m/s, corresponding to an energy of(1980 ± 80) cm-1, by simple modifications to the setup. Prior to collision, the molecules can be laser- prepared in different vibrational and rotational quantum states. State- selective detection of the scattering products makes it possible to determine the quantum state, the scattering angle, and the kinetic energy of the scattered molecules. Therefore, detailed information about the scattering process can be obtained. The design of the machine allows for flexible laser access near the surface, such that a variety of different preparation and detection schemes can be employed. Ultra-high vacuum conditions in the scattering chamber are achieved by baking the entire apparatus, including the decelerator and the hexapole. Because of the carrier gas removal and a total of three differential pumping stages, no pressure rise is detected in the scattering chamber due to the incident molecular beam. Scattering experiments of CO (a3Π) on Au(111) have been performed. The scattering process leads to electron emission because the metastable excitation energy exceeds the work function of the surface. The electron emission yield, i.e. the number of electrons emitted per incident metastable particle, has been measured to be 0.13 ± 0.05. A laser ionization-depletion method is used which makes it possible to directly compare the intensity of the metastable CO ionization signal to the intensity decrease of the electron emission signal. It was also shown that vibrationally excited metastable CO leads to a higher electron emission yield. By preparing different vibrational distributions of CO in the a3Π electronic state via Franck-Condon pumping, the electron emission yield was determined for groups of vibrational levels. The first three vibrationally excited levels have an increased electron emission yield which on average is a factor of 1.5 larger than that of the vibrational ground state. Averaged over the vibrational levels with quantum number v = 4, 5, 6 , this factor is approximately 2.6 . In the range between 93 m/s and 512 m/s, the electron emission was observed to be independent of the velocity of the incident molecules. When the surface temperature is raised from 250 K to 900 K, the intensity of the electron emission signal increases by 27 %. These results are not in agreement with the models currently used to describe the de-excitation of electronically excited molecules at metal surfaces. This demonstrates the need for more theoretical work to incorporate the role of vibration into the description of the de-excitation mechanism.
Slowing down atoms using laser cooling, together with techniques like magnetic trapping and evaporative cooling, has led to numerous exciting results over the last decade [1], with the realization of Bose-Einstein condensation as the most spectacular achievement [2]. Laser-cooling schemes are applicable to atoms since closed multilevel systems can be realized and many consecutive absorptionemission cycles can be induced. This leads to a significant momentum transfer from the photons of the laser to the atom, resulting in a change of the velocity of the atom. There currently is a great interest in producing cold molecules for the study of cold molecule-molecule collisions, molecular quantum collective effects, Doppler-free spectroscopy, frequency standards, as well as many other applications already realized for atoms [3]. Slowing down of neutral molecules, a prerequisite for being able to trap them, has proven to be considerably more difficult to be achieved, however. The above-mentioned laser-cooling scheme cannot be applied to slow down molecules as no simple closed-level systems can be found; the unavoidable off-resonant radiative decay of molecules from the excited state to other vibrational levels in the electronic ground state hampers efficient momentum transfer [4]. Once molecules are present at sufficiently low kinetic energies, below a fraction of a cm21, they can be trapped in various ways. Trapping of neutral molecules in inhomogeneous magnetic [3] and electric fields [5] and trapping based on the use of evanescent fields close to the dielectricvacuum interface have been proposed [6]. It has also been suggested that extremely high laser powers might be used to induce a dipole moment in polarizable molecules, leading to trapping of these molecules in the laser beam [7]. Other methods to produce slow molecules have been put forward and have recently been successfully applied to produce the first samples of trapped molecules. By injecting molecules in a cold buffer gas, sufficiently low kinetic energies of the injected molecules can be obtained after thermalization that they can subsequently be trapped in an inhomogeneous magnetic field. This has recently been demonstrated for CaH injected in 3He buffer gas at temperatures of around 0.3 K [8]. Associative collisions between ultracold trapped atoms [9] have proven to be