We calculate the microwave spectra of ultracold KRb alkali metal dimers, including hyperfine interactions and in the presence of electric and magnetic fields. We show that microwave transitions may be used to transfer molecules between different hyperfine states, but only because of the presence of nuclear quadrupole interactions. Hyperfine splittings may also complicate the use of ultracold molecules for quantum computing. The spectrum of molecules oriented in electric fields may be simplified dramatically by applying a simultaneous magnetic field.
We investigate the microwave spectra of ultracold alkali metal dimers in magnetic, electric and combined fields, taking account of the hyperfine structure due to the nuclear spins. We consider the molecules 41K87Rb and 7Li133Cs, which are the targets of current experiments and demonstrate two extremes of large and small nuclear quadrupole coupling. We calculate the frequencies and intensities of transitions that may be used to transfer ultracold molecules between hyperfine states in a magnetic field, employing different polarizations of microwave radiation. In an electric field, the hyperfine …
The effect of conical intersections (CIs) on electronic relaxation, transitions from excited states to ground states, is well studied, but their influence on hyperfine quenching in a reactant molecule is not known. Here, we report on ultracold collision dynamics of the hydroxyl free-radical OH with Sr atoms leading to quenching of OH hyperfine states. Our quantum-mechanical calculations of this process reveal that quenching is efficient due to anomalous molecular dynamics in the vicinity of the conical intersection at collinear geometry. We observe wide scattering resonance features in both el…
Ultracold molecular collisions in magnetic fields: Efficient incorporation of hyperfine structure in the total rotational angular momentum representation
We investigate the effect of hyperfine interactions on ultracold molecular collisions in magnetic fields, using ^{24}Mg(^1S) + ^{14}NH(^3Sigma^-) as a prototype system. We explore the energy and magnetic field dependence of the cross sections, comparing the results with previous calculations that neglected hyperfine interactions (Phys. Rev. Lett. 103, 183201 (2009)). The main effect of hyperfine interactions for spin relaxation cross sections is that the kinetic energy release of the dominant outgoing channels does not reduce to zero at low fields. This results in reduced centrifugal suppressi…
While attaining external field control of bimolecular chemical reactions has long been a coveted goal of physics and chemistry, the role of hyperfine interactions and dc magnetic fields in achieving such control has remained elusive. We develop an extended coupled-channel statistical theory of barrierless atom-diatom chemical reactions, and apply it to elucidate the effects of magnetic fields and hyperfine interactions on the ultracold chemical reaction Li($^2\text{S}_{1/2}$) + CaH($^2Σ^+$) $\to$ LiH($^1Σ^+$) + Ca($^1\text{S}_{0}$) on a newly developed set of ab initio potential energy surface…
We demonstrate coherent microwave control of rotational and hyperfine states of trapped, ultracold, and chemically stable $^{23}$Na$^{40}$K molecules. Starting with all molecules in the absolute rovibrational and hyperfine ground state, we study rotational transitions in combined magnetic and electric fields and explain the rich hyperfine structure. Following the transfer of the entire molecular ensemble into a single hyperfine level of the first rotationally excited state, $J{=}1$, we observe collisional lifetimes of more than $3\, \rm s$, comparable to those in the rovibrational ground state…
Recently it has been shown that pairs of atoms can form metastable bonds due to non-conservative forces induced by dissipation [Lemeshko&Weimer, Nature Comm. 4, 2230 (2013)]. Here we study the dynamics of interaction-induced coherent population trapping - the process responsible for the formation of dissipatively bound molecules. We derive the effective dissipative potentials induced between ultracold atoms by laser light, and study the time evolution of the scattering states. We demonstrate that binding occurs on short timescales of ~10 microseconds, even if the initial kinetic energy of the …
We demonstrate that it is possible to efficiently control ultracold chemical reactions of alkali-metal atoms colliding with open-shell alkali-metal dimers in their metastable triplet states by choosing the internal hyperfine and rovibrational states of the reactants as well as by inducing magnetic Feshbach resonances with an external magnetic field. We base these conclusions on coupled-channel statistical calculations that include the effects of hyperfine contact and magnetic-field-induced Zeeman interactions on ultracold chemical reactions of hyperfine-resolved ground-state Na and the triplet…
We report on the creation of an ultracold dipolar gas of fermionic $^{23}$Na$^{40}$K molecules in their absolute rovibrational and hyperfine ground state. Starting from weakly bound Feshbach molecules, we demonstrate hyperfine resolved two-photon transfer into the singlet ${\rm X}^1Σ^+ |v{=}0,J{=}0\rangle$ ground state, coherently bridging a binding energy difference of 0.65 eV via stimulated rapid adiabatic passage. The spin-polarized, nearly quantum degenerate molecular gas displays a lifetime longer than 2.5 s, highlighting NaK's stability against two-body chemical reactions. A homogeneous …
We have studied the effects of chirped femtosecond laser pulses on the formation of ultracold molecules in a Rb magneto-optical trap. We have found that application of chirped femtosecond pulses suppressed the formation of 85Rb-2 and 87Rb-2 lowest triplet state molecules in contrast to comparable non-chirped pulses, cw illumination, and background formation rates. Variation of the amount of chirp indicated that this suppression is coherent in nature, suggesting that coherent control is likely to be useful for manipulating the dynamics of ultracold quantum molecular gases.
We investigate the energy levels of heteronuclear alkali metal dimers in levels correlating with the lowest rotational level of the ground electronic state, which are important in efforts to produce ground-state ultracold molecules. We use density-functional theory to calculate nuclear quadrupole and magnetic coupling constants for RbK and RbCs and explore the hyperfine structure in the presence of electric and magnetic fields. For nonrotating states, the zero-field splittings are dominated by the electron-mediated part of the nuclear spin-spin coupling. They are a few kHz for RbK isotopologs …
Magnetic Feshbach resonances play a central role in experimental research of atomic gases at ultracold temperatures, as they allow one to control the microscopic interactions between ultracold atoms by tuning an applied magnetic field. These resonances arise due to strong hyperfine interactions between the unpaired electron and the nuclear magnetic moment of the alkali metal atoms. A major thrust of current research is to create an ultracold gas of diatomic alkali-metal molecules in the ground rovibrational state of the ground electronic $^1Σ$ state. Unlike alkali metal atoms, $^1Σ$ diatomic m…
We present elastic and inelastic spin-changing cross sections for cold and ultracold NH($X\,^3Σ^-$) + NH($X\,^3Σ^-$) collisions, obtained from full quantum scattering calculations on an accurate \textit{ab initio} quintet potential-energy surface. Although we consider only collisions in zero field, we focus on the cross sections relevant for magnetic trapping experiments. It is shown that evaporative cooling of both fermionic $^{14}$NH and bosonic $^{15}$NH is likely to be successful for hyperfine states that allow for s-wave collisions. The calculated cross sections are very sensitive to the …
Resonances in ultracold collisions involving heavy molecules are difficult to understand, and have proven challenging to detect. Here we report the observation of magnetically tunable Feshbach resonances in ultracold collisions between $^{23}$Na$^{40}$K molecules in the rovibrational ground state and $^{40}$K atoms. We prepare the atoms and molecules in various hyperfine levels of their ground states and observe the loss of molecules as a function of the magnetic field. The atom-molecule Feshbach resonances are identified by observing an enhancement of the loss rate coefficients. We have obser…
Advances in atomic, molecular, and optical (AMO) physics techniques allowed the cooling of simple molecules down to the ultracold regime ($\lesssim$ 1 mK), and opened the opportunities to study chemical reactions with unprecedented levels of control. This review covers recent developments in studying bimolecular chemistry at ultralow temperatures. We begin with a brief overview of methods for producing, manipulating, and detecting ultracold molecules. We then survey experimental works that exploit the controllability of ultracold molecules to probe and modify their long-range interactions. Fur…
Ultracold collisions between Cs atoms and Cs2 dimers in the electronic ground state are observed in an optically trapped gas of atoms and molecules. The Cs2 molecules are formed in the triplet ground state by cw-photoassociation through the outer well of the 0g-(P3/2) excited electronic state. Inelastic atom-molecule collisions converting internal excitation into kinetic energy lead to a loss of Cs2 molecules from the dipole trap. Rate coefficients are determined for collisions involving Cs atoms in either the F=3 or F=4 hyperfine ground state and Cs2 molecules in either highly vibrationally e…
Two-color photoassociation of ground state $^6$Li$^{87}$Rb molecules via the $\mathrm{B}^1Π$ electronic state using short pulses near a magnetic Feshbach resonance is studied theoretically. A near-resonant magnetic field is applied to mix the hyperfine singlet and triplet components of the initial wave function and enhance the photoassociation rate, before the population is transferred to the ground state by a second pulse. We show that an increase of up to three orders of magnitude in the absolute number of molecules produced is attainable for deeply bound vibrational levels. This technique c…
Multichannel quantum defect theory (MQDT) has been widely applied to resonant and non-resonant scattering in a variety of atomic collision processes. In recent years, the method has been applied to cold collisions with considerable success, and it has proven to be a computationally viable alternative to full-close coupling (CC) calculations when spin, hyperfine and external field effects are included. In this paper, we describe a hybrid approach for molecule-molecule scattering that includes the simplicity of MQDT while treating the short-range interaction explicitly using CC calculations. Thi…
We have calculated elastic and state-resolved inelastic cross sections for cold and ultracold collisions in the Rb($^1 S$) + OH($^2 Π_{3/2}$) system, including fine-structure and hyperfine effects. We have developed a new set of five potential energy surfaces for Rb-OH($^2 Π$) from high-level {\em ab initio} electronic structure calculations, which exhibit conical intersections between covalent and ion-pair states. The surfaces are transformed to a quasidiabatic representation. The collision problem is expanded in a set of channels suitable for handling the system in the presence of electric a…
We show that isotope-exchange reactions between ground-state alkali-metal, alkaline-earth-metal, and lanthanide heteronuclear dimers consisting of two isotopes of the same atom are exothermic with an energy change in the range of 1-8000$\,$MHz thus resulting in cold or ultracold products. For these chemical reactions there are only one rovibrational and at most several hyperfine possible product states. The number and energetics of open and closed reactive channels can be controlled by the laser and magnetic fields. We suggest a laser-induced isotope- and state-selective Stark shift control to…
Understanding and controlling collisions is crucial to the burgeoning field of ultracold molecules. All experiments so far have observed fast loss of molecules from the trap. However, the dominant mechanism for collisional loss is not well understood when there are no allowed 2-body loss processes. Here we experimentally investigate collisional losses of nonreactive ultracold RbCs molecules, and compare our findings with the sticky collision hypothesis that pairs of molecules form long-lived collision complexes. We demonstrate that loss of molecules occupying their rotational and hyperfine gro…
We have performed high resolution photoassociation spectroscopy of rubidium ultra long-range Rydberg molecules in the vicinity of the 25$P$ state. Due to the hyperfine interaction in the ground state perturber atom, the emerging mixed singlet-triplet potentials contain contributions from both hyperfine states. We show that this can be used to induce remote spin-flips in the perturber atom upon excitation of a Rydberg molecule. When furthermore the spin-orbit splitting of the Rydberg state is comparable to the hyperfine splitting in the ground state, the orbital angular momentum of the Rydberg …
Single-molecule magnets (SMMs) are promising elements for quantum informatics. In the presence of strong magnetic anisotropy, they exhibit magnetization blocking - a magnetic memory effect at the level of a single molecule. Recent studies have shown that the SMM performance scales with the height of magnetization blocking barrier. By employing molecular engineering this can be significantly modified, remaining independent from other external factors such as magnetic field. Taking advantage of hyperfine coupling of electronic and nuclear spins further enhances their functionality, however, a po…
