We measure inelastic cross sections for atomic thorium (Th) and molecular thorium monoxide (ThO) in collisions with $^3$He at temperatures near 1 K. We determine the Zeeman relaxation cross section for Th ($^3$F$_2$) to be $\sim 2 \times 10^{-17}$~cm$^{-2}$ at 800~mK. We study electronic inelastic processes in Th ($^3$P$_0$) and find no quenching even after $10^6$ collisions at 800~mK. We measure the vibrational quenching cross section for ThO~(X,~$\nu=1$) to be $(7.9 \pm 2.7) \times 10^{-19}$~cm$^{-2}$ at 800~mK. Finally, we observe indirect evidence for ThO (X, $\nu=0$)--$^3$He van der Waals complex formation, and measure the 3-body recombination rate constant to be $\Gamma_3 = (8 \pm 2) \times 10^{-33}$~cm$^6$s$^{-1}$ at 2.4~K. The stability of the ground Th ($^3$F$_2$) state, metastable Th ($^3$P$_0$) state, and vibrational excited ThO (X, $\nu=1$) state provides data on anisotropic interactions in new systems and opens up the possibility for further studies and experiments, including trapping. / Physics

This thesis describes the design, construction, operation, and characterisation of an experimental apparatus that produces a source of internally cold, slow molecules that can be used for studying ion-molecule reactions at low temperatures. The apparatus combines buffer-gas cooling with a bent quadrupole velocity selector to cool both the translational and rotational degrees of freedom of the molecules. A cold cell (6 K) is filled with a buffer gas, such as helium, that exhibits sufficiently high vapour pressure for cryogenic applications. Hot molecules (150 to 300 K) enter the cell and thermalise with the buffer gas through collisions. Molecules are subsequently loaded into an electrostatic quadrupole guide, which acts as a velocity filter; only translationally cold polar molecules are guided around the bend. Using a buffer-gas-cooled source of molecules for electrostatic velocity selection, rather than a 300 K effusive source, yields a rotationally cold sample, with J ≤ 3. This rotational selectivity will enable the dependence of reaction cross sections on the reactant rotational state to be examined. Mass spectrometry is used to characterise cold molecular beams of ND3 and CH3F, while (2+1) REMPI spectra are recorded for the ammonia isotopologues. The peak velocity of guided ND3 is 75.86(0.70) ms-1 for standard conditions in a 6 K helium buffer gas cell (1.0 sccm ND3 flow rate, 0.6 mbar helium inlet pressure, ± 5 kV voltage). This corresponds to a peak kinetic energy of 6.92(0.13) K. (2+1) REMPI spectroscopy of the B1E''(v2'=5) ← X(1) transition enabled the rotational state distribution of guided ammonia molecules to be established. PGOPHER simulations of the experimental spectra suggest a rotational temperature of 10 K for ND3 molecules (from a 6 K helium buffer gas cell). The extent of translational and rotational cooling can be controlled by varying the molecular and buffer gas densities within the cell, by changing the temperature of the buffer gas cell (we can operate at 6 K or 17 K), or by changing the buffer gas. The translational temperature of guided ND3 is similar in a 6 K helium and 17 K neon buffer gas cell (peak kinetic energies of 6.92(0.13) K and 5.90(0.01) K, respectively) because the heavier neon gas has a slightly lower thermal velocity at 17 K than helium does at 6 K. Despite similar translational temperatures, the rotational temperature of guided ND3 is lower for molecules exiting the 6 K helium cell compared to the 17 K neon buffer gas cell (10 K and 15 K, respectively). The 6 K helium and 17 K neon buffer gas cells provide an excellent opportunity to investigate the effect of rotational cooling on branching ratios and reaction rates in low temperature ion-molecule reactions. The buffer gas cell and velocity guide described in this work will be combined with a linear Paul ion trap, to facilitate the study of cold ion-molecule reactions.

Inelastic collision processes driven by anistropic interactions are investigated below 1 K. Three distinct experiments are presented. First, for the atomic species antimony (Sb), rapid relaxation is observed in collisions with \(^4He\). We identify the relatively large spin-orbit coupling as the primary mechanism which distorts the electrostatic potential to introduce significant anisotropy to the ground \(^4S_{3/2}\) state. The collisions are too rapid for the experiment to fix a specific value, but an upper bound is determined, with the elastic-to-inelastic collision ratio \(\gamma \leq 9.1 x 10^2\). In the second experiment, inelastic \(\mathcal{m}_J\)-changing and \(J\)-changing transition rates of aluminum (Al) are measured for collisions with \(^3He\). The experiment employs a clean method using a single pump/probe laser to measure the steady-state magnetic sublevel population resulting from the competition of optical pumping and inelastic collisions. The collision ratio \(\gamma\) is measured for both \(\mathcal{m}_J\)- and \(J\)-changing processes as a function of magnetic field and found to be in agreement with the theoretically calculated dependence, giving support to the theory of suppressed Zeeman relaxation in spherical \(^2P_{1/2}\) states [1]. In the third experiment, very rapid atom-atom relaxation is observed for the trapped lanthanide rare-earth atoms erbium (Er) and thulium (Tm). Both are nominally nonspherical \((L \neq 0)\) atoms that were previously observed to have strongly suppressed electronic interaction anisotropy in collisions with helium \((\gamma > 10^4-10^5, [2,3])\). No suppression is observed in collisions between these atoms \((\gamma \lesssim 10)\), which likely implies that evaporative cooling them in a magnetic trap will be impossible. Taken together, these studies reveal more of the role of electrostatic anisotropy in cold atomic collisions. / Physics

We cool and study trans-Stilbene, Nile Red and Benzonitrile in a cryogenic (7K) cell filled with low density helium buffer gas. No molecule-helium cluster formation is observed, indicating limited atom-molecule sticking in this system. We place an upper limit of 5% on the population of clustered He-trans-Stilbene, consistent with a measured He-molecule collisional residence time of less than \(1 \mu s\). With several low energy torsional modes, trans-Stilbene is less rigid than any molecule previously buffer gas cooled into the Kelvin regime. We report cooling and gas phase visible spectroscopy of Nile Red, a much larger molecule. Our data suggest that buffer gas cooling will be feasible for a variety of small biological molecules. The same cell is also ideal for studying collisional relaxation cross sections. Measurements of Benzonitrile vibrational state decay results in determination of the vibrational relaxation cross sections of \(\sigma_{22} = 8x10^{-15} cm^2\) and \(\sigma_{21} = 6x10^{-15} cm^2\) for the 22 (v=1) and 21 (v=1) states. For the first time, we directly observe formation of cold molecular dimers in a cryogenic buffer gas cell and determine the dimer formation cross section to be \(\sim10^{-13} cm^2\). / Physics