Advances in atomic physics have led to the possibility of a coherent transformation between ultra-cold atoms and molecules including between completely bosonic condensates. Such transformations are enabled by the magneto-association of atoms at a Feshbach resonance which results in a passage through a quantum critical point. In this study, we show that the presence of generic interaction between the constituent atoms and molecules can fundamentally alter the nature of the critical point, change the yield of the reaction and the order of the consequent phase transition. We find that the correlations introduced by this interaction induce nontrivial many-body physics such as coherent oscillations between atoms and molecules, and a selective formation of squeezed molecular quantum states and quantum cat states. We provide analytical and numerical descriptions of these effects, along with scaling laws for the reaction yield in non-adiabatic regimes.
We study the reaction kinetics of chemical processes occurring in the ultracold regime and systematically investigate their dynamics. Quantum entanglement is found to play a key role in driving an ultracold reaction towards a dynamical equilibrium. In case of multiple concurrent reactions Hamiltonian chaos dominates the phase space dynamics in the mean field approximation.
Chemical chain reactions are known to enable extremely sensitive detection schemes in chemical, biological, and medical analysis, and have even been used in the search for dark matter. Here we show that coherent, ultracold chemical reactions harbor great potential for quantum metrology: In an atom-molecule Bose-Einstein condensate (BEC), a weak external perturbation can modify the reaction dynamics and lead to the coherent creation of molecules in an atom-dominant regime which can be selectively detected with modern spectroscopic techniques. This promises to substantially improve the viability…
Chemical reactions at ultracold temperature provide an ideal platform to study chemical reactivity at the fundamental level, and to understand how chemical reactions are governed by quantum mechanics. Recent years have witnessed the remarkable progress in studying ultracold chemistry with ultracold molecules. However, these works were limited to exothermic reactions. The direct observation of state-to-state ultracold endothermic reaction remains elusive. Here we report on the investigation of endothermic and nearly thermoneutral atom-exchange reactions in an ultracold atom-dimer mixture. By de…
Ultracold molecules offer remarkable opportunities to study chemical reactions at nearly zero temperature. Although significant progresses have been achieved in exploring ultracold bimolecular reactions, the investigations are usually limited to measurements of the overall loss rates of the reactants. Detection of the reaction products will shed new light on understanding the reaction mechanism and provide a unique opportunity to study the state-to-state reaction dynamics. Here we report on the direct observation of an exoergic atom-exchange reaction in an ultracold atom-dimer mixture. Both th…
Chemical reaction rates often depend strongly on stereodynamics, namely the orientation and movement of molecules in three-dimensional space. An ultracold molecular gas, with a temperature below 1 uK, provides a highly unusual regime for chemistry, where polar molecules can easily be oriented using an external electric field and where, moreover, the motion of two colliding molecules is strictly quantized. Recently, atom-exchange reactions were observed in a trapped ultracold gas of KRb molecules. In an external electric field, these exothermic and barrierless bimolecular reactions, KRb+KRb -> …
Reactive or elastic two-body collisions in an ultracold gas are affected by quantum statistics. In this paper, we study ensemble-averaged collision rates for a two-species fermionic gas. The two species may have different masses, densities and temperatures. We investigate how averaged collision rates are affected by the presence of Fermi spheres in the initial states; Pauli blocking of final states is not considered. It is shown that, independently on the details of the collision, Fermi-averaged collision rates deviate from Boltzmann-averaged ones, particularly for a gas with strong imbalance …
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…
In an ultracold, optically trapped mixture of $^{87}$Rb and metastable triplet $^4$He atoms we have studied trap loss for different spin-state combinations, for which interspecies Penning ionization is the main two-body loss process. We observe long trapping lifetimes for the purely quartet spin-state combination, indicating strong suppression of Penning ionization loss by at least two orders of magnitude. For the other spin-mixtures we observe short lifetimes that depend linearly on the doublet character of the entrance channel. We compare the extracted loss rate coefficient with recent predi…
We report on three-body recombination of a single trapped Rb^+ ion and two neutral Rb atoms in an ultracold atom cloud. We observe that the corresponding rate coefficient K_3 depends on collision energy and is about a factor of 1000 larger than for three colliding neutral Rb atoms. In the three-body recombination process large energies up to several 0.1eV are released leading to an ejection of the ion from the atom cloud. It is sympathetically recooled back into the cloud via elastic binary collisions with cold atoms. Further, we find that the final ionic product of the three-body processes is…
Controlling the pathways and outcomes of reactions is a broadly pursued goal in chemistry. In gas phase reactions, this is typically achieved by manipulating the properties of the reactants, including their translational energy, orientation, and internal quantum state. In contrast, here we influence the pathway of a reaction via its intermediate complex, which is generally too short-lived to be affected by external processes. In particular, the ultracold preparation of potassium-rubidium (KRb) reactants leads to a long-lived intermediate complex (K$_2$Rb$_2^*$), which allows us to steer the re…
We present a unified formalism for describing chemical reaction rates of trapped, ultracold molecules. This formalism reduces the scattering to its essential features, namely, a propagation of the reactant molecules through a gauntlet of long-range forces before they ultimately encounter one another, followed by a probability for the reaction to occur once they do. In this way, the electric-field dependence should be readily parametrized in terms of a pair of fitting parameters (along with a $C_6$ coefficient) for each asymptotic value of partial wave quantum numbers $|L,M \rangle$. From this,…
Studying chemical reactions on a state-to-state level tests and improves our fundamental understanding of chemical processes. For such investigations it is convenient to make use of ultracold atomic and molecular reactants as they can be prepared in well defined internal and external quantum states$^{1-4}$. In general, even cold reactions have many possible final product states$^{5-15}$ and reaction channels are therefore hard to track individually$^{16}$. In special cases, however, only a single reaction channel is essentially participating, as observed e.g. in the recombination of two atoms …
Femtochemistry techniques have been instrumental in accessing the short time scales necessary to probe transient intermediates in chemical reactions. Here we take the contrasting approach of prolonging the lifetime of an intermediate by preparing reactant molecules in their lowest ro-vibronic quantum state at ultralow temperatures, thereby drastically reducing the number of exit channels accessible upon their mutual collision. Using ionization spectroscopy and velocity-map imaging of a trapped gas of potassium-rubidium molecules at a temperature of 500~nK, we directly observe reactants, interm…
The spectrum of two bosons and two fermions in a trap is calculated using a correlated-Gaussian basis throughout the range of a broad Fano-Feshbach resonance. The calculations provide a few-body solution to the magneto-association of fermionic Feshbach molecules. This solution is used to study the time evolution of the system as the scattering length changes, mimicking experiments with Bose-Fermi mixtures near Fano-Feshbach resonances. The structure of avoided crossings in the few-body spectrum enables an interpretation of the dynamics of the system as a sequence of Landau-Zener transitions. T…
We propose a method to suppress the chemical reactions between ultracold bosonic ground-state $^{23}$Na$^{87}$Rb molecules based on optical shielding. By applying a laser with a frequency blue-detuned from the transition between the lowest rovibrational level of the electronic ground state $X^1Σ^+ (v_X=0, j_X=0)$, and the long-lived excited level $b^3Π_0 (v_b=0, j_b=1)$, the long-range dipole-dipole interaction between the colliding molecules can be engineered, leading to a dramatic suppression of reactive and photoinduced inelastic collisions, for both linear and circular laser polarizations.…
How does a chemical reaction proceed at ultralow temperatures? Can simple quantum mechanical rules such as quantum statistics, single scattering partial waves, and quantum threshold laws provide a clear understanding for the molecular reactivity under a vanishing collision energy? Starting with an optically trapped near quantum degenerate gas of polar $^{40}$K$^{87}$Rb molecules prepared in their absolute ground state, we report experimental evidence for exothermic atom-exchange chemical reactions. When these fermionic molecules are prepared in a single quantum state at a temperature of a few …
The control of the ultracold collisions between neutral atoms is an extensive and successful field of study. The tools developed allow for ultracold chemical reactions to be managed using magnetic fields, light fields and spin-state manipulation of the colliding particles among other methods. The control of chemical reactions in ultracold atom-ion collisions is a young and growing field of research. Recently, the collision energy and the ion electronic state were used to control atom-ion interactions. Here, we demonstrate spin-controlled atom-ion inelastic processes. In our experiment, both sp…
Collisional resonances are an important tool which has been used to modify interactions in ultracold gases, for realizing novel Hamiltonians in quantum simulations, for creating molecules from atomic gases and for controlling chemical reactions. So far, such resonances have been observed for atom-atom collisions, atom-molecule collisions and collisions between Feshbach molecules which are very weakly bound. Whether such resonances exist for ultracold ground state molecules has been debated due to the possibly high density of states and/or rapid decay of the resonant complex. Here we report a v…
We study cold heteronuclear atom ion collisions by immersing a trapped single ion into an ultracold atomic cloud. Using ultracold atoms as reaction targets, our measurement is sensitive to elastic collisions with extremely small energy transfer. The observed energy-dependent elastic atom-ion scattering rate deviates significantly from the prediction of Langevin but is in full agreement with the quantum mechanical cross section. Additionally, we characterize inelastic collisions leading to chemical reactions at the single particle level and measure the energy-dependent reaction rate constants. …
The realization of ultracold polar molecules in laboratories has pushed both physics and chemistry to new realms. In particular, these polar molecules offer scientists unprecedented opportunities to explore chemical reactions in the ultracold regime where quantum effects become profound. However, a key question about how two-body losses depend on quantum correlations in an interacting many-body system remains open so far. Here, we present a number of universal relations that directly connect two-body losses to other physical observables, including the momentum distribution and density correlat…
The creation of ultracold molecules is currently limited to diatomic species. In this letter we present a theoretical description of the photoassociation of ultracold atoms and molecules to create ultracold excited triatomic molecules, thus being a novel example of light-assisted ultracold chemical reaction. The calculation of the photoassociation rate of ultracold Cs atoms with ultracold Cs$_2$ molecules in their rovibrational ground state is reported, based on the solution of the quantum dynamics involving the atom-molecule long-range interactions, and assuming a model potential for the shor…
We present and analyze a toolbox for the controlled manipulation of ultracold polar molecules, consisting of detection of molecules, atom-molecule entanglement, and engineering of dissipative dynamics. Our setup is based on fast chemical reactions between molecules and atoms leading to a quantum Zeno-based collisional blockade in the system. We demonstrate that the experimental parameters for achieving high fidelities can be found using a straightforward numerical optimization. We exemplify our approach for a system comprised of NaK molecules and Na atoms and we discuss the consequences of res…
Chemical reactions can be surprisingly efficient at ultracold temperatures ( < 1mK) due to the wave nature of atoms and molecules. The study of reactions in the ultracold regime is a new research frontier enabled by cooling and trapping techniques developed in atomic and molecular physics. In addition, ultracold molecular gases that offer diverse molecular internal states and large electric dipolar interactions are sought after for studies of strongly interacting many-body quantum physics. Here we propose a new approach for producing ultracold molecules in the absolute internal and motional qu…
Quantum mechanics is an inherently linear theory. However, collective effects in many body quantum systems can give rise to effectively nonlinear dynamics. In the present work, we analyze whether and to what extent such nonlinear effects can be exploited to enhance the rate of quantum evolution. To this end, we compute a suitable version of the quantum speed limit for numerical and analytical examples. We find that the quantum speed limit grows with the strength of the nonlinearity, yet it does not trivially scale with the ``degree'' of nonlinearity. This is numerically demonstrated for the pa…
The loss of ultracold trapped atoms due to deeply inelastic reactions has previously been taken into account in effective field theories for low-energy atoms by adding local anti-Hermitian terms to the effective Hamiltonian. Here we show that when multi-atom systems are considered, an additional modification is required in the equation governing the density matrix. We define an effective density matrix by tracing over the states containing high-momentum atoms produced by deeply inelastic reactions. We show that it satisfies a Lindblad equation, with local Lindblad operators determined by the l…
Ultracold polar molecules offer the possibility of exploring quantum gases with interparticle interactions that are strong, long-range, and spatially anisotropic. This is in stark contrast to the dilute gases of ultracold atoms, which have isotropic and extremely short-range, or "contact", interactions. The large electric dipole moment of polar molecules can be tuned with an external electric field; this provides unique opportunities such as control of ultracold chemical reactions, quantum information processing, and the realization of novel quantum many-body systems. In spite of intense exper…
We present investigations of the formation rate and collisional stability of lithium Feshbach molecules in an ultracold three-component mixture composed of two resonantly interacting fermionic 6-Li spin states and bosonic 174-Yb. We observe long molecule lifetimes (> 100 ms) even in the presence of a large ytterbium bath and extract reaction rate coefficients of the system. We find good collisional stability of the mixture in the unitary regime, opening new possibilities for studies and probes of strongly interacting quantum gases in contact with a bath species.
We have studied the associative ionization of a Rydberg atom and a ground state atom in an ultracold Rydberg gas. The measured scattering cross section is three orders of magnitude larger than the geometrical size of the produced molecule. This giant enhancement of the reaction kinetics is due to an efficient directed mass transport which is mediated by the Rydberg electron. We also find that the total inelastic scattering cross section is given by the geometrical size of the Rydberg electron's wavefunction.
We investigate the effect of far-off-resonant trapping light on ultracold bosonic RbCs molecules. We use kHz-precision microwave spectroscopy to measure the differential AC Stark shifts between the ground and first excited rotational levels of the molecule with hyperfine-state resolution. We demonstrate through both experiment and theory that coupling between neighboring hyperfine states manifests in rich structure with many avoided crossings. This coupling may be tuned by rotating the polarization of the linearly polarized trapping light. A combination of spectroscopic and parametric heating …
We show that the effect of measurement back-action results in the generation of multiple many-body spatial modes of ultracold atoms trapped in an optical lattice, when scattered light is detected. The multipartite mode entanglement properties and their nontrivial spatial overlap can be varied by tuning the optical geometry in a single setup. This can be used to engineer quantum states and dynamics of matter fields. We provide examples of multimode generalizations of parametric down-conversion, Dicke, and other states, investigate the entanglement properties of such states, and show how they ca…
Periodically-driven quantum systems are currently explored in view of realizing novel many-body phases of matter. This approach is particularly promising in gases of ultracold atoms, where sophisticated shaking protocols can be realized and inter-particle interactions are well controlled. The combination of interactions and time-periodic driving, however, often leads to uncontrollable heating and instabilities, potentially preventing practical applications of Floquet-engineering in large many-body quantum systems. In this work, we experimentally identify the existence of parametric instabiliti…
We report the full control over the internal states of ultracold $^{23}$Na$^{87}$Rb molecules, including vibrational, rotational and hyperfine degrees of freedom. Starting from a sample of weakly bound Feshbach molecules, we realize the creation of molecules in single hyperfine levels of both the rovibrational ground and excited states with a high-efficiency and high-resolution stimulated Raman adiabatic passage. Starting from the rovibrational and hyperfine ground state, we demonstrate rotational and hyperfine control with one- and two-photon microwave spectroscopy. This achievement of fully …
Ultracold gases of three distinguishable particles with large scattering lengths are expected to show rich few-body physics related to the Efimov effect. We have created three different mixtures of ultracold 6Li atoms and weakly bound 6Li2 dimers consisting of atoms in three different hyperfine states and studied their inelastic decay via atom-dimer collisions. We have found resonant enhancement of the decay due to the crossing of Efimov-like trimer states with the atom-dimer continuum in one mixture as well as minima of the decay in another mixture, which we interpret as a suppression of exch…
Three-body recombination is a prime example of the fundamental interaction between three particles. Due to the complexity of this process it has resisted a comprehensive description. Experimental investigations have mainly focussed on the observation of corresponding loss rates without revealing information on the reaction products. Here, we provide the first general experimental study on the population distribution of molecular quantum states after three-body recombination in a non-resonant regime. We have developed a highly sensitive detection scheme which combines photoionization of the mol…
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 report the creation of ultracold bosonic $^{23}$Na$^{87}$Rb Feshbach molecules via magneto-association. By ramping the magnetic field across an interspecies Feshbach resonance, at least 4000 molecules can be produced out of the near degenerate ultracold mixture. Fast loss due to inelastic atom-molecule collisions is observed, which limits the pure molecule number, after residual atoms removal, to 1700. The pure molecule sample can live for 21.8(8) ms in the optical trap, long enough for future molecular spectroscopy studies toward coherently transferring to the singlet ro-vibrational ground…
Understanding the sources of losses and chemical reactions of ultracold alkali-metal molecules is among the critical elements needed for their application in precision measurements and quantum technologies. Recent experiments with nonreactive systems have reported unexpectedly large loss rates, posing a challenge for theoretical explanation. Here, we examine the dynamics of intermediate four-atom complexes formed in bimolecular collisions. We calculate the nuclear spin--rotation, spin--spin, and quadrupole coupling constants for bialkali tetramers using ab intio quantum-chemical methods. We sh…
We study the evolution of a single BaRb$^+$ molecule while it continuously collides with ultracold Rb atoms. The initially weakly-bound molecule can undergo a sequence of elastic, inelastic, reactive, and radiative processes. We investigate these processes by developing methods for discriminating between different ion species, electronic states, and kinetic ion energy ranges. By comparing the measurements to model calculations we obtain a consistent description of the typical trajectory of the ion through the manifold of available atomic and molecular states. As a further result, we determine …
The control of chemical reactions is a recurring theme in physics and chemistry. Traditionally, chemical reactions have been investigated by tuning thermodynamic parameters, such as temperature or pressure. More recently, physical methods such as laser or magnetic field control have emerged to provide completely new experimental possibilities, in particular in the realm of cold collisions. The control of reaction pathways is also a critical component to implement molecular quantum information processing. For these undertakings, single particles provide a clean and well-controlled experimental …
We report the successful production of an ultracold sample of absolute ground-state $^{23}$Na$^{87}$Rb molecules. Starting from weakly-bound Feshbach molecules formed via magneto-association, the lowest rovibrational and hyperfine level of the electronic ground state is populated following a high efficiency and high resolution two-photon Raman process. The high purity absolute ground-state samples have up to 8000 molecules and densities of over $10^{11}$ cm$^{-3}$. By measuring the Stark shifts induced by external electric fields, we determined the permanent electric dipole moment of the absol…
The collision of molecules at ultracold temperatures is of great importance for understanding the chemical interactions at the quantum regime. While much theoretical work has been devoted to this, experimental data are only available sparsely mainly due to the difficulty in producing ground-state molecules at ultracold temperatures. We report here the creation of optically trapped samples of ground-state bosonic sodium-rubidium molecules with precisely controlled internal states and, enabled by this, a detailed study on the inelastic loss with and without the NaRb + NaRb $\rightarrow$ Na$_2$ +…
We consider collisional studies of linear polyatomic ions immersed in ultracold atomic gases and investigate the intermolecular interactions and chemical reactions of several molecular anions ($\mathrm{OH}^-$, $\mathrm{CN}^-$, $\mathrm{NCO}^-$, $\mathrm{C}_2\mathrm{H}^-$, $\mathrm{C}_4\mathrm{H}^-$) with alkali-metal (Li, Na, K, Rb, Cs) and alkaline-earth-metal (Mg, Ca, Sr, Ba) atoms. State-of-the-art ab initio techniques are applied to compute the potential energy surfaces (PESs) for these systems. The coupled cluster method restricted to single, double, and noniterative triple excitations, C…
We investigate the energy dependence and the internal-state dependence of the charge-exchange collision cross sections in a mixture of $^6$Li atoms and $^{40}$Ca$^+$ ions in the collision energy range from 0.2 mK to 1 K. Deliberately excited ion micromotion is used to control the collision energy of atoms and ions. The energy dependence of the charge-exchange collision cross section obeys the Langevin model in the temperature range of the current experiment, and the measured magnitude of the cross section is correlated to the internal state of the $^{40}$Ca$^+$ ions. Revealing the relationship…
We investigate collisional loss in an ultracold mixture of $^{40}$K$^{87}$Rb molecules and $^{87}$Rb atoms, where chemical reactions between the two species are energetically forbidden. Through direct detection of the KRb$_{2}^{*}$ intermediate complexes formed from atom-molecule collisions, we show that a $1064$ nm laser source used for optical trapping of the sample can efficiently deplete the complex population via photo-excitation, an effect which can explain the universal two-body loss observed in the mixture. By monitoring the time-evolution of the KRb$_{2}^{*}$ population after a sudden…
We present a novel method for probing the alignment of the molecular axis of an ultracold, nonpolar dimer. These results are obtained using diatomic $^{87}\textrm{Rb}_2$ molecules in the vibrational ground state of the lowest triplet potential $a^3Σ_u^+$ trapped in a 3D optical lattice. We measure the molecular polarizabilities, which are directly linked to the alignment, along each of the $x$, $y$, and $z$ directions of the lab coordinate system. By preparing the molecules in various, precisely defined rotational quantum states we can control the degree of alignment of the molecular axis with…
We present a time-independent quantum formalism to describe the dynamics of molecules with permanent electric dipole moments in a two-dimensional confined geometry such as a one-dimensional optical lattice, in the presence of an electric field. Bose/Fermi statistics and selection rules play a crucial role in the dynamics. As examples, we compare the dynamics of confined fermionic and bosonic polar KRb molecules under different confinements and electric fields. We show how chemical reactions can be suppressed, either by a "statistical suppression" which applies for fermions at small electric fi…
Universal collision rate constants are calculated for ultracold collisions of two like bosonic or fermionic heteronuclear alkali-metal dimers involving the species Li, Na, K, Rb, or Cs. Universal collisions are those for which the short range probability of a reactive or quenching collision is unity such that a collision removes a pair of molecules from the sample. In this case, the collision rates are determined by universal quantum dynamics at very long range compared to the chemical bond length. We calculate the universal rate constants for reaction of the reactive dimers in their ground vi…
Reaction-diffusion models are common in many areas of statistical physics, where they describe the late-time dynamics of chemical reactions. Using a Bose gas representation, which maps the real-time dynamics of the reactants to the imaginary-time evolution of an interacting Bose gas, we consider corrections to the late-time scaling of $k$-particle annihilation processes $k A \to \emptyset$ above the upper critical dimension, where mean-field theory sets the leading order. We establish that the leading corrections are not given by a small renormalization of the reaction rate due to $k$-particle…
Ultracold YbAg molecules have been recently proposed as promising candidates for electron electric dipole moment searches [Verma, Jayich, and Vutha, Phys. Rev. Lett. 125, 153201 (2020)]. Here, we calculate potential energy curves, permanent electric dipole and quadrupole moments, and static electric dipole polarizabilities for the YbCu, YbAg, and YbAu molecules in their ground electronic states. We use the coupled cluster method restricted to single, double, and noniterative triple excitations with large Gaussian basis sets, while the scalar relativistic effects are included within the small-c…
We provide a brief commentary on recent work by Hammer and Son on the scaling behavior of nuclear reactions involving the emission of several loosely bound neutrons. In this work they discover a regime, termed unnuclear physics, in which these reactions are governed by an approximate conformal symmetry of the nuclear force. Remarkably, the scaling exponents that govern nuclear reactions can be related to the energies of ultracold atomic drops confined in harmonic potentials. We also comment on the importance and the limitations of this approximate symmetry in the physics of neutron stars.
