Cold molecules promise to reveal a rich set of novel collision dynamics in the low-energy regime. By combining for the first time the techniques of Stark deceleration, magnetic trapping, and cryogenic buffer gas cooling, we present the first experimental observation of cold collisions between two different species of state-selected neutral polar molecules. This has enabled an absolute measurement of the total trap loss cross sections between OH and ND(3) at a mean collision energy of 3.6 cm(-1) (5 K). Due to the dipolar interaction, the total cross section increases upon application of an external polarizing electric field. Cross sections computed from ab initio potential energy surfaces are in agreement with the measured value at zero external electric field. The theory presented here represents the first such analysis of collisions between a (2)Π radical and a closed-shell polyatomic molecule.
Cold molecules promise to reveal a rich set of novel collision dynamics in the low-energy regime. By combining for the first time the techniques of Stark deceleration, magnetic trapping, and cryogenic buffer gas cooling, we present the first experimental observation of cold collisions between two different species of state-selected neutral polar molecules. This has enabled an absolute measurement of the total trap loss cross sections between OH and ND(3) at a mean collision energy of 3.6 cm(-1) (5 K). Due to the dipolar interaction, the total cross section increases upon application of an external polarizing electric field. Cross sections computed from ab initio potential energy surfaces are in agreement with the measured value at zero external electric field. The theory presented here represents the first such analysis of collisions between a (2)Π radical and a closed-shell polyatomic molecule.
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.
Cold polar molecules offer fascinating prospects for ultracold chemistry and quantum physics. However, their inherent collision properties remain largely unknown, as it seems fundamentally impossible to reach sufficiently low energies by merging two beams of molecules with substantial dipole moments. Here we report measurements of state-to-state cross-sections for collisions between ammonia isotopologues at energies between 0.3 and 100 cm−1 using an advanced beam-merging protocol. We experimentally observed a local maximum in the cross-sections, which indicates that the dipole moments can switch off at low collision energies. Scattering calculations reproduced this maximum in good agreement and explained the observed scaling with the molecule’s parity splitting energies. Measurements of the correlated energy transfer in both collision partners yielded direct evidence of the suppression of the dipole–dipole interaction at low energies. Our results demonstrate how collisions between an important class of polar molecules evolve from high temperatures towards the ultracold regime in a counterintuitive way, and offer distinctive opportunities to control cold molecular collisions with external fields. Interactions between polar molecules are expected to become increasingly strong at low collision energies through dipole–dipole forces. Now it has been shown that ammonia molecules instead exhibit suppressed dipolar interactions in the cold regime as the dipole moment effectively switches off, as shown by local maxima in the collision cross-sections.
In this dissertation, I present ab initio theoretical results on cold and ultra-cold collision of atomic and molecular systems with magnetic and electric dipole moments. The collisions of different isotopes of maximally spin-polarized chromium atoms (52Cr and 53Cr), alkali-metal atom (Rb) - chromium atom, and magnetically trapped hydroxide (OH) with cold supersonic helium beam are considered in this thesis. Spin-changing cross sections and rate constants in Cr-Cr isotopic collision in the presence of a magnetic field are calculated by propagating a set of multichannel equations in the field. The coupling between dipole-dipole allowed and hyperfine channels are included. The short range electrostatic interactions between atoms and atom-molecule are represented with highly-accurate Born-Oppenheimer (BO) potential energy curves. Due to the large spin multiplicity in Cr-Cr and Rb-Cr interactions, more than the usual singlet and triplet channels are obtained. The long-range van der Waals (vdW) interactions between atoms are calculated, for Cr, by including accurate transition frequencies, discrete dipole matrix elements, and photoionization continuum oscillator strengths, and for Rb, using published dynamic polarizabilities. The vdW coefficients for Cr-Cr and Rb-Cr are obtained. In the cold collision regime, I investigate the influence of angular momentum shape resonances on the elastic and inelastic (loss channel) rate coefficients, and when the Zeeman relaxation, resulting in the loss of atoms from the trap, dominates elastic collision. Dipolar collisions are crucial to achieving quantum degeneracy. Magnetically tuned Fano-Feshbach closed-channel resonances are used to obtain zero-energy scattering lengths in comparison with observation of trap loss. In bosonic chromium collisions, resonances appear due only to dipolar interaction. The interplay between hyperfine and dipolar resonances in mixed-species Cr-Cr and Rb-Cr collisions is studied. In Rb-Cr, it is found that the molecule has broken symmetry and therefore contains a large permanent electric dipole moment in the ground state. A recent collisional experiment at JILA of a supersonic helium beam with a magnetically trapped OH radical found the onset of a quantum threshold in the total OH loss rate. Using ab initio BO energy surfaces, I calculated the spin-changing collisions which removed OH from the trap. Only after including the effect of the trapping potential on the collision dynamics, some agreement with observation was found. ^
Cold collisions of polyatomic molecular radicals with S-state atoms in a magnetic field: An ab initio study of He + CH2(X~) CH 2(X) collisions
We develop a rigorous quantum mechanical theory for collisions of polyatomic molecular radicals with S-state atoms in the presence of an external magnetic field. The theory is based on a fully uncoupled space-fixed basis set representation of the multichannel scattering wave function. Explicit expressions are presented for the matrix elements of the scattering Hamiltonian for spin-1/2 and spin-1 polyatomic molecular radicals interacting with structureless targets. The theory is applied to calculate the cross sections and thermal rate constants for spin relaxation in low-temperature collisions of the prototypical organic molecule methylene [CH(2)(X(3)B(1))] with He atoms. To this end, two accurate three-dimensional potential energy surfaces (PESs) of the He-CH(2)(X(3)B(1)) complex are developed using the state-of-the-art coupled-cluster method including single and double excitations along with a perturbative correction for triple excitations and large basis sets. Both PESs exhibit shallow minima and are weakly anisotropic. Our calculations show that spin relaxation in collisions of CH(2), CHD, and CD(2) molecules with He atoms occurs at a much slower rate than elastic scattering over a large range of temperatures (1 μK-1 K) and magnetic fields (0.01-1 T), suggesting excellent prospects for cryogenic helium buffer-gas cooling of ground-state ortho-CH(2)(X(3)B(1)) molecules in a magnetic trap. Furthermore, we find that ortho-CH(2) undergoes collision-induced spin relaxation much more slowly than para-CH(2), which indicates that magnetic trapping can be used to separate nuclear spin isomers of open-shell polyatomic molecules.
We report a combined experimental and theoretical study of collision-induced dipolar relaxation in a cold spin-polarized gas of atomic nitrogen (N). We use buffer gas cooling to create trapped samples of 14N and 15N atoms with densities $(5\ifmmode\pm\else\textpm\fi{}2)\ifmmode\times\else\texttimes\fi{}{10}^{12} {\mathrm{cm}}^{\ensuremath{-}3}$ and measure their magnetic relaxation rates at milli-Kelvin temperatures. These measurements, together with rigorous quantum scattering calculations based on accurate ab initio interaction potentials for the ${}^{7}{\ensuremath{\Sigma}}_{u}^{+}$ electronic state of N2 demonstrate that dipolar relaxation in N+N collisions occurs at a slow rate of $~{10}^{\ensuremath{-}13} {\mathrm{cm}}^{3}$/s over a wide range of temperatures (1 mK to 1 K) and magnetic fields (10 mT to 2 T). The calculated dipolar relaxation rates are insensitive to small variations of the interaction potential and to the magnitude of the spin-exchange interaction, enabling the accurate calibration of the measured N atom density. We find consistency between the calculated and experimentally determined rates. Our results suggest that N atoms are promising candidates for future experiments on sympathetic cooling of molecules.
Collisions between cold polar molecules represent a fascinating research frontier but have proven hard to probe experimentally. We report measurements of inelastic cross sections for collisions between nitric oxide (NO) and deuterated ammonia (ND 3 ) molecules at energies between 0.1 and 580 centimeter −1 , with full quantum state resolution. At energies below the ~100-centimeter −1 well depth of the interaction potential, we observed backward glories originating from peculiar U-turn trajectories. At energies below 0.2 centimeter −1 , we observed a breakdown of the Langevin capture model, which we interpreted in terms of a suppressed mutual polarization during the collision, effectively switching off the molecular dipole moments. Scattering calculations based on an ab initio NO-ND 3 potential energy surface revealed the crucial role of near-degenerate rotational levels with opposite parity in low-energy dipolar collisions.