Using the example of the $\mathrm{S}{\mathrm{O}}_{2}$ molecule, we will discuss photodissociation at threshold as a possibility for producing cold molecules or atoms. The fragments SO and O have low excess energy and are free radicals with high interest for applications like cold chemistry. The threshold behavior is tunable by external fields and shows great similarity to Feshbach resonance studies in cold atom collisions. To take full advantage of the cold fragmentation, it is necessary to dissociate within a cold sample of molecules. In our initial experiments we have demonstrated substantial Stark deceleration of $\mathrm{S}{\mathrm{O}}_{2}$.
Using the example of the SO2 molecule, we will discuss photodissociation at threshold as a possibility for producing cold molecules or atoms. The fragments SO and O have low excess energy and are free radicals with high interest for applications like cold chemistry. The threshold behavior is tunable by external fields and shows great similarity to Feshbach resonance studies in cold atom collisions. To take full advantage of the cold fragmentation, it is necessary to dissociate within a cold sample of molecules. In our initial experiments we have demonstrated substantial Stark deceleration of SO2.
We produce SO2 molecules with a centre of mass velocity near zero using a Stark decelerator. Since the initial kinetic energy of the supersonic SO2 molecular beam is high, and the removed kinetic energy per stage is small, 326 deceleration stages are necessary to bring SO2 to a complete standstill, significantly more than in other experiments. We show that in such a decelerator possible loss due to coupling between the motional degrees of freedom must be considered. Experimental results are compared with 3D Monte-Carlo simulations and the quantum state selectivity of the Stark decelerator is demonstrated.
Samples of cold and ultracold polar molecules have the potential to revolutionize physical chemistry, precision measurement, and few-body quantum physics. This thesis describes experimental results for the production of cold samples of OH radicals by Stark deceleration of a supersonic beam. Since Stark deceleration cannot increase the phase space density of the sample, the initial production stage of the OH molecule is critical. The first set of experiments describes a general methodology for the production of OH beams with maximal phase space density, as well as the subsequent coupling to a Stark decelerator. Additionally, we describe the redesign of our electrostatic trap, optimized for future collision experiments of OH with co-trapped ultracold Rb atoms. The new design resulted in a 15-fold increase in total number of trapped molecules over the previous design when tested with ND3 molecules. The second set of experiments focuses on laser-based detection of OH molecules at the exit of the decelerator based on laser induced fluorescence (LIF) and resonance enhanced multiphoton ionizaton (REMPI). The latter method uses vacuum-ultraviolet light at 118nm produced by third-harmonic generation in Xe/Ar gas mixtures as the ionizing step. The sensitivity of this latter technique is limited by the attainable photon flux of the ionizing radiation at 118nm. We present detailed measurements of the conversion efficiencies as well as absolute photon fluxes. Strategies to overcome these limitations as well as prospects for detection of OH molecules in a trap are discussed.
This thesis describes the development of a relatively novel technique for the gen- eration and subsequent trapping of cold species. Molecules in a pulsed supersonic expansion are photolysed, such that the centre-of-mass velocity vector of one of the fragments is equal in magnitude but opposed in orientation to the lab-frame velocity of the precursor molecule. This technique, known as ‘Photostop’, leaves a fraction of the fragments with a narrow velocity distribution, centered around zero velocity in the lab-frame. They can be shown to have zero velocity by changing the time between photodissociation and ionisation; fragments with a high kinetic energy will leave the ionisation volume prior to interrogation. The underlying velocity distribu- tion is uncovered by using the velocity-map imaging technique, and the temperature of the fragments can be determined.The method was originally optimised for the molecular case. Cold NO has been produced from the dissociation of NO₂ molecules, and a single rotational state has been shown to remain in the ionisation volume 10 μs after dissociation, implying a sample temperature of 1.17 K. Using the optimised experimental conditions de- rived from the velocity cancellation of NO, the atomic case is demonstrated for the dissociation of Br₂ to give zero-velocity Br fragments. The Br atoms are seen for delay times in excess of 100 μs, showing the greater applicability of the method to the atomic case. The temperature of the residual atoms is shown to be in the milliKelvin regime, as determined through detailed Monte Carlo simulation of the motion of the stopped atoms. The possibility of trapping the ultracold Br atoms in a magnetic field is explored, and a quadrupolar trap created between two per- manent bar magnets is demonstrated to confine the atoms spatially, within the ion extraction optics, for delays in excess of 1 ms.The Photostop technique is intended to be a stepping stone on the way to widening the number of chemical species available for study in the ultracold regime. The possibility of improvements to the experiment is considered, in order to increase the efficiency of the experiment such that the number density becomes high enough to be viable as a source of atoms for use in cold chemical reactive studies. The possibility of extending the method so as to be used as a tunable velocity source of atoms is also discussed.
The development of techniques to cool/slow and trap atoms and molecules brought about a revolution in atomic and molecular physics, with an impact on physics in large. When slowed/cooled down, atoms and molecules become matter waves whose properties differ vastly from those of thermal matter. In particular, close to absolute zero temperature, the interaction range of atoms or molecules increases far beyond their dimensions, imparting to them highly desirable collective and collisional properties. The latter have been predicted to give rise to a novel ultracold chemistry. The article describes the main techniques of producing cold molecules, both the indirect ones (photoassociation of cold atoms, collisional association of cold atoms controlled via Feshbach resonances) and the direct techniques (buffer-gas cooling, Stark deceleration and others). Ongoing and anticipated future experiments with cold molecules are reviewed, including pioneering ventures aimed at radiative lifetime measurements, reduction of transit time broadening, measurements of ultracold collisional cross-sections, and testing of fundamental symmetries in nature, such as the time-reversal symmetry and parity.
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.
The use of photodissociation to produce cold, slow molecules from a molecular beam of cold, fast molecules is dubbed “photostop”. The essence of the scheme is thus: a pulsed molecular beam of a precursor molecule AB seeded in a noble carrier gas is crossed by a laser beam. The laser light dissociates AB, producing fragments A and B. These recoil from the dissociation site. The speed of the molecular beam and the wavelength of the laser beam are tuned so that the recoil velocity of those A molecules recoiling opposite to the molecular beam direction cancels out their initial velocity. This leaves a certain amount of A close to stationary in the laboratory frame. The photostop technique was first demonstrated with the production of cold, slow NO radicals by the photodissociation of nitrogen dioxide, both at Durham and in South Korea. The work described in this thesis began as a development of the NO photostop experiment, with an attempt made to magnetically trap NO. Latterly, the photostop project became part of the Millikelvin Molecules in a Quantum Array (MMQA) collaboration, the aim of which is the trapping of ten million cold, polar molecules. To this end, the photostop of SH radicals by the photodissociation of hydrogen disulphide was demonstrated.