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Deceleration and trapping of polyatomic molecules

Manish Vashishta

Published Jan 1, 2020• 0 citations
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Abstract

In this dissertation, substantial headway towards the Zeeman deceleration and magnetic trapping of methyl radicals, and AC Stark trapping of ammonia are presented. Notably, the first ever trapping of gaseous methyl radicals within a permanent magnetic trap is discussed in detail. Additionally, the use of a counter rotating nozzle to produce slow polyatomic molecular beam is discussed. The methyl radical is the smallest and most stable paramagnetic intermediate hydrocarbon species, and as such, the physicochemical properties of this species are of substantial interest to astrochemists and organic chemists alike. Methyl radical, being a paramagnetic molecule, is decelerated using an 85 coil Zeeman decelerator from 320 m/s to 60 m/s. Notably, the first ever trapping of methyl radicals in the gas phase inside a permanent magnetic trap is described here. The trapped radicals had a temperature of 200 mK, and a lifetime of greater than one second. Lastly, the collisional loss cross sections for the methyl radical with helium and argon are also reported. In addition to the magnetic trapping of the methyl radical, progress towards the trapping of polar molecules with microwave radiation is discussed in detail. A quality (abbr. Q) factor of 5 x 105 was achieved by cooling a Fabry Perot cavity with superconducting mirror surfaces to 3 K. Resulting from the large Q factor, the maximum electric field inside the cavity is 1 MV/m when a power input of 10 W is used. At this electric field, ammonia molecules travelling slower than 10 m/s can be successfully trapped. Additionally, the AC stark shift of ammonia molecules within the trap is reported as the first step towards their trapping. Lastly, a counter rotating nozzle was constructed based on the design presented by Strebel et al. at the University of Freiburg. The technical modifications presented in this thesis yielded an increase in the density of the molecular beam by two orders of magnitude, in comparison to the Freiburg design. This nozzle was used to decelerate acetone from 430 m/s to 110 m/s, and unlike the Stark and Zeeman decelerators, it can be used to decelerate any gaseous molecules.

DOI
10.14288/1.0390918

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•Jan 1, 2006•1 citation
In this dissertation, substantial headway towards the Zeeman deceleration and magnetic trapping of methyl radicals, and AC Stark trapping of ammonia are presented. Notably, the first ever trapping of gaseous methyl radicals within a permanent magnetic trap is discussed in detail. Additionally, the use of a counter rotating nozzle to produce slow polyatomic molecular beam is discussed. The methyl radical is the smallest and most stable paramagnetic intermediate hydrocarbon species, and as such, the physicochemical properties of this species are of substantial interest to astrochemists and organic chemists alike. Methyl radical, being a paramagnetic molecule, is decelerated using an 85 coil Zeeman decelerator from 320 m/s to 60 m/s. Notably, the first ever trapping of methyl radicals in the gas phase inside a permanent magnetic trap is described here. The trapped radicals had a temperature of 200 mK, and a lifetime of greater than one second. Lastly, the collisional loss cross sections for the methyl radical with helium and argon are also reported. In addition to the magnetic trapping of the methyl radical, progress towards the trapping of polar molecules with microwave radiation is discussed in detail. A quality (abbr. Q) factor of 5 x 105 was achieved by cooling a Fabry Perot cavity with superconducting mirror surfaces to 3 K. Resulting from the large Q factor, the maximum electric field inside the cavity is 1 MV/m when a power input of 10 W is used. At this electric field, ammonia molecules travelling slower than 10 m/s can be successfully trapped. Additionally, the AC stark shift of ammonia molecules within the trap is reported as the first step towards their trapping. Lastly, a counter rotating nozzle was constructed based on the design presented by Strebel et al. at the University of Freiburg. The technical modifications presented in this thesis yielded an increase in the density of the molecular beam by two orders of magnitude, in comparison to the Freiburg design. This nozzle was used to decelerate acetone from 430 m/s to 110 m/s, and unlike the Stark and Zeeman decelerators, it can be used to decelerate any gaseous molecules.
We have demonstrated that a supersonic beam of methyl radicals (CH_{3}) in the ground rotational state of both para and ortho species has been slowed down to standstill with a magnetic molecular decelerator, and successfully captured spatially in an anti-Helmholtz magnetic trap for >1 s. The trapped CH_{3} radicals have a mean translational temperature of about 200 mK with an estimated density of >5.0×10^{7} cm^{-3}. The methyl radical is an ideal system for the study of cold molecules not only because of its high reactivities at low temperatures, but also because further cooling below 1 mK is plausible via sympathetic cooling with ultracold atoms. The demonstrated trapping capability of methyl radicals opens up various possibilities for realizing ultracold ensembles of molecules towards Bose-Einstein condensation of polyatomic molecules and investigations of reactions governed by quantum statistics.
Collisions between cold polyatomic molecules and atoms are essential in various processes, including interstellar chemical reactions, quantum tunneling, and precision measurements.The methyl radical was the rst polyatomic radical trapped in a magnetic trap. This was achieved by our group in 2017, where the trapped radicals were trapped at a temperature of approximately 130 mK. The methyl radical has been proposed as a potential candidate for sympathetic cooling, which can achieve temperatures below 1 mK. In order to elucidate the collisional properties of the methyl radical, collisions between magnetically trapped, cold methyl radicals, and room temperature helium and argon atoms were investigated experimentally. This work presents the results of these collisional studies and their comparison with theoretically derived trap loss rates. Quantum diffractive collisions dominate the collisions between room temperature helium atoms and cold methyl radicals in a magnetic trap with a trap depth of about 134 mK. More than 10 % of trap loss is attributed to inelastic collisions, in which the methyl radicals are excited to a rotationally excited state. On the other hand, collisions between cold methyl radicals and room temperature argon at this trap depth is near the border between quantum diffractive collisions and classical collisions.
Research in the field of cold polar molecules is progressing rapidly. An array of interesting\ntopics is being developed including precision measurement and fundamental tests, quantum phase transitions, and ultracold chemistry. In particular, dipolar molecules in well-defined quantum states enable exquisite control of their interactions via applied electric fields. The long-range, anisotropic interaction between dipolar molecules leads to new collision dynamics that could be used for novel collective effects, quantum state engineering, and information processing. The focus of this Thesis is the production of cold samples of neutral OH molecules via Stark deceleration and magnetic trapping for novel collision experiments. This novelty results from our combination of cold external beams and trapped target molecules which facilitates observation of dipolar effects as well as low temperature collision resonances. The large permanent electric dipole moment of OH allows us to precisely tune the lab-frame velocity of the molecular packets from ∼ 500 m/s to rest. We have magnetically trapped OH packets at the terminus of our Stark decelerator at a temperature of 70 mK and density of 106 cm−3. With improved understanding of Stark deceleration, we optimize the decelerator efficiency and its coupling to the magnetic trap. Our latest trap design uses permanent ring magnets to create a three-dimensional magnetic quadrupole field. Use of magnetically trapped OH molecules for collision experiments with external beams allow us the unique opportunity of observing both elastic and inelastic collisions. In addition, the trap confinement yields sensitivity to differential elastic cross sections at low collision energies. This open magnetic trap has allowed measurement of collision cross sections between trapped OH and external supersonic beams of He and D2, the latter of which is of astrophysical interest due to the role of H2-OH collisions in pumping interstellar OH megamasers. The combination of trapped OH molecules and temperature tuned beams of He and D2 has facilitated measurement of the lowest-energy D2-OH collision cross sections yet reported. More recently, we report the first observation of electric-field dependent cross sections between two different species of cold polar molecules - OH and ND3 - thereby demonstrating control over molecular scattering in the cold regime. By combining for the first time the production techniques of Stark deceleration and buffer gas cooling, we increase the molecular interaction time by∼ 105 over traditional crossed-beam experiments to gain enhanced sensitivity at the characteristic densities of cold molecule production.
Successful magnetic trapping of both SH at a density of 2.4 x 10^5 cm^-3 and atomic oxygen at a density of 3000 +/- 900 cm^-3 has been demonstrated with respective trapping lifetimes of 40 +/- 10 ms and 82 +/- 3 ms inside a 0.41 T deep, anti-Helmholtz configuration magnetic trap. To achieve trapping of these species, a stable precursor was cooled by supersonic expansion in a molecular beam and photodissociated in such a way as to match and oppose a photofragments recoil speed to the precursors molecular beam speed. This process is called photostop. Velocity-map images have been taken of photostop of atomic oxygen from photodissociation of NO2 in a molecular beam. They show that atomic oxygen can be photostopped from a variety of NO photodissociation co-fragments with a suitably broad molecular-beam velocity-distribution. Although photostop is simple and cheap to use, the trapping lifetimes and densities that have been achieved in this thesis are not competitive compared to other methods of trapping similar molecular species. The main problem that presents universally in photostop experiments is due to the large number of fast molecules from the supersonic expansion that pass through the trap after the photostop event. Only a small fraction of the molecules in the molecular beam are stopped and the remaining ones cause significant trap loss through high energy elastic collisions with trapped species. Work has been carried out to develop the cavity-enhanced laser-induced-fluorescence (CELIF) technique to be used more widely in the cold molecules field. The technique was employed unsuccessfully to measure photostopped SH radicals but was used elsewhere to measure cold SD radicals after Stark deceleration. In addition, the technique has been initially developed for use inside magnetic traps. Clusters of NO.Ar(n) have been studied using [1+1'] REMPI to assess the viability of a new soft-ionisation technique for molecular clusters of atmospheric interest. This work did not show conclusive evidence that [1+1'] REMPI would reduce cluster fragmentation and displayed some interesting but poorly understood data.
Control of the translational motion of methyl radicals is demonstrated by using pulsed magnetic fields created by a series of solenoid coils. By synchronously switching the magnetic fields corresponding to the motion of the radicals, we have observed the deceleration and focusing of a supersonic radical beam. The present result shows that Zeeman deceleration of polyatomic free radicals in the doublet state can be realized. This opens possibilities for trapping cold polyatomic free radicals in a spatially confined area leading to further studies of cold collisions and reactions.
Cold molecules are potentially beneficial for several areas of research. They have applications in spectroscopy, collision studies and, for instance, the study of the effects of dipole-dipole interactions in BECs. One method to decelerate and thereby cool down neutral dipolar molecules is to use a Stark decelerator. In my thesis, I show the advantages of cold, Stark-decelerated molecules in a high-resolution spectroscopy experiment, using the pure inversion motion of ammonia molecules. The transition associated with this motion is measured both on a warm and on a cold beam, resulting in an increased resolution in the latter case. For many of the applications of cold molecules mentioned above, molecules in high-field seeking states are necessary. To induce molecules to form a BEC, ground state molecules, which are always high-field seeking, are necessary for the use of preliminary cooling methods like evaporative cooling, as trap loss due to inelastic collisions is absent in this state. Many of the more interesting spectroscopy experiments, like experiments with biomolecules or experiments involved with the testing of fundamental physics theories, need to be performed on heavy molecules. Most states in these molecules are high-field seeking as well. To be able to better study high-field seeking molecules, it is important that we are able to confine a cold sample of such molecules in a trap. For this, a so-called AC trap is needed. The first electrical AC trap for molecules is demonstrated in this thesis. It utilizes two fields that are shaped like a saddle point. One of the fields is rotated over 90 degrees with respect to the other. By switching between these two fields, a molecule will alternately experience a focusing (maximum in the electric field strength) and defocusing force (minimum in the electric field strength) in each direction. At the appropriate switching frequency, the overall force is focusing and the molecules remain trapped