Collisions between ultracold calcium monohydroxide (CaOH) molecules are realized and studied. Inelastic collision rate constants are measured for CaOH prepared in ground and excited vibrational states, and the electric field dependence of these rates is measured for molecules in single quantum states of the parity-doubled bending mode. Theoretical calculations of collision rate coefficients are performed and found to agree with measured values. The lowest collisional loss rates are for states with repulsive long-range potentials that shield ultracold molecules from loss channels at short distance. These results unveil the collisional behavior of parity doublet molecules in the ultracold regime, and lay the foundation for future experiments to evaporatively cool polyatomic molecules to quantum degeneracy.

Accurate ab initio potential energy surfaces are essential to understand and predict collisional outcomes in ultracold molecular systems. In this study, we explore the intermolecular interactions between two laser-cooled CaF molecules, in both their ground and excited electronic states, aiming to understand the mechanisms behind the observed collisional losses on the nonreactive, spin-polarized surface of the CaF+CaF system. Using state-of-the-art ab initio methods, we compute 12 electronic states of the Ca2F2 complex within the rigid rotor approximation applied to CaF. Calculating the potential energy surfaces for the excited electronic states of Ca2F2 is challenging and computationally expensive. Our approach employs the multireference configuration interaction method, restricted to single and double excitations, along with a reasonably large active space to ensure the convergence in the excited states. We also compute the spin-orbit coupling between the ground state and the lowest spin-polarized triplet state, as well as the spin-spin coupling within the lowest triplet state (1) 3A'. Additionally, we determine the electric transition dipole moments for the (1) 3A'-(2) 3A' and (1) 3A'-(1) 3A'' transitions. Notably, we find that the lowest spin-polarized state (1) 3A', shifted by 1064 nm of laser light from the optical dipole trap, intersects several electronically excited states. Finally, by analyzing the potential energy surfaces, we discuss two plausible pathways that may account for the observed collisional losses on the spin-polarized surface of the CaF+CaF system.

We discuss the influence of collisions on the dynamics of an ultracold gas whose constituents interact via dipolar forces. This dynamics is governed by the elastic scattering cross section of the molecules, which is to some extent under the experimentalist's control. We compare side-by-side several different situations, highlighting their similarities and differences. These situations are collisions between: 1) point dipoles; 2) electric-field-shielded polar molecules; and 3) microwave-shielded polar molecules, including the effect of microwave ellipticity.

Long-range and anisotropic dipolar interactions profoundly modify the dynamics of particles hopping in a periodic lattice potential. We report the realization of a generalized t-J model with dipolar interactions using a system of ultracold fermionic molecules with spin encoded in the two lowest rotational states. We independently tuned the dipolar Ising and spin-exchange couplings and the molecular motion and studied their interplay on coherent spin dynamics. Using Ramsey spectroscopy, we observed and modeled interaction-driven contrast decay that depends strongly both on the strength of the anisotropy between Ising and spin-exchange couplings and on motion. This study paves the way for future exploration of kinetic spin dynamics and quantum magnetism with highly tunable molecular platforms in regimes that are challenging for existing numerical and analytical methods.

Energy transfer between different mechanical degrees of freedom in atom-molecule collisions has been studied and largely understood. However, systems involving spins remain less explored. In this study, we directly observed energy transfer from atomic hyperfine to molecular rotation in the 87Rb ( ∣ F a , M F a = ∣ 2 , 2 ) + 40K87Rb (X1Σ+, rotational state N = 0) ⟶ Rb ( ∣ 1 , 1 ) + KRb (N = 0, 1, 2) collision with state-to-state precision. We also performed quantum scattering calculations that rigorously included the coupling between spin and rotational degrees of freedom at short range under the assumption of rigid-rotor KRb monomers moving along a single potential energy surface. The calculated product rotational state distribution deviates from the observations even after extensive tuning of the atom-molecule potential energy surface. In addition, our ab initio calculations indicate that spin-rotation coupling is enhanced close to a conical intersection that is energetically accessible at short range. This, together with the deviation, suggests that vibrational degrees of freedom and conical intersections play an important part in the coupling. Our observations confirm that spin is coupled to mechanical rotation at short range and establish a benchmark for future theoretical studies.

We study the fully itinerant dynamics of ultracold but nondegenerate polar molecules with a spin-1/2 degree of freedom encoded into two of their electric field dressed rotational states. Center-of-mass molecular motion is constrained to two dimensions via tight confinement with a one-dimensional optical lattice, but remains mostly unconstrained within the plane. The pseudospins can become entangled through ultracold dipolar collisions, for which the locality of interactions is greatly relaxed by free molecular motion. At the level of single-molecule observables, collision-induced entanglement manifests as spin decoherence, for which our theoretical calculations serve well to describe recent Ramsey contrast measurements of quasi-two-dimensional confined KRb molecules at JILA [A. Carroll et al., Science 388, 6745 (2025)]. In presenting a more detailed theoretical analysis of the KRb experiment, we highlight a key finding that molecular loss enhanced by particle exchange symmetry can lead to a suppression of collective spin decoherence, a mechanism we refer to as "loss-induced quantum autoselection." We then show that, by utilizing bialkali species with sufficiently large dipole moments, loss can be near completely suppressed in all collision channels via electric field tunable confinement-induced collisional shielding. The afforded collisional stability permits fully coherent spin mixing dynamics, natively realizing unitary circuit dynamics with random all-to-all connectivity and U(1) charge conservation. This work establishes a bridge between the domains of ultracold molecular collisions and many-body spin physics, ultimately proposing the use of nondegenerate bulk molecular gases as a controllable platform for nonequilibrium explorations of itinerant quantum matter.

We predict the existence of stable bound states between pairs of ultracold diatomic molecules with the aid of a static electric field and 1D harmonic confinement. We focus on collisions of NaK-NaK identical fermions, for which we find that currently achievable experimental parameters allow the observation of these confinement-induced field-linked bound states as scattering resonances. The bound state is highly stable with lifetimes estimated to be tens of seconds long. With the diatomic molecules bound at distances a fraction of the dipolar length scale, these complexes allow for explorations of polyatomic chemistry and Fermi gas superfluid pairing.

We study anisotropic thermalization in dilute gases of microwave shielded polar molecular fermions. For collision energies above the threshold regime, we find that thermalization is suppressed due to a strong preference for forward scattering and a reduction in total cross section with energy, significantly reducing the efficiency of evaporative cooling. We perform close-coupling calculations on the effective potential energy surface derived by Deng et al. [Phys. Rev. Lett. 130, 183001 (2023)], to obtain accurate 2-body elastic differential cross sections across a range of collision energies. We use Gaussian process regression to obtain a global representation of the differential cross section, over a wide range of collision angles and energies. The route to equilibrium is then analyzed with cross-dimensional rethermalization experiments, quantified by a measure of collisional efficiency toward achieving thermalization.

In the quest toward realizing novel quantum matter in ultracold molecular gases, we perform a numerical study of evaporative cooling in ultracold gases of microwave-shielded polar fermionic molecules. Our Monte Carlo simulations incorporate accurate two-body elastic and inelastic scattering cross sections, realistic modeling of the optical dipole trap, and the influence of Pauli blocking at low temperatures. The simulations are benchmarked against data from evaporation studies performed with ultracold NaK molecules, showing excellent agreement. We further explore the prospects for optimizing the evaporation efficiency by varying the ramp rate and duration of the evaporation trajectory. Our simulation shows that it is possible to reach <10% of the Fermi temperature under optimal conditions even in the presence of two-body molecular losses.

We theoretically investigate the merging behaviour of two identical supersolids through dipolar Bose-Einstein condensates confined within a double-well potential. By adiabatically tuning the barrier height and the spacing between the two wells for specific trap aspect ratios, the two supersolids move toward each other and lead to the emergence of a variety of ground state phases, including a supersolid state, a macrodroplet state, a ring state, and a labyrinth state. We construct a phase diagram that characterizes various states seen during the merging transition. Further, we calculate the force required to pull the two portions of the gas apart, finding that the merged supersolids act like a deformable plastic material. Our work paves the way for future studies of layer structure in dipolar supersolids and the interaction between them in experiments.

The probability distributions of the real and imaginary parts of atomic scattering lengths a are derived, in a two-channel model that allows for inelastic scattering to occur. While the real part of a remains Cauchy-distributed, as predicted for single channel scattering in the classic work of Gribakin and Flambaum, the imaginary part of a is seen to be strongly peaked near zero. Two-body inelastic scattering rates may therefore be smaller in general than a naive estimate would suggest.

We consider collective motion and damping of dipolar Fermi gases in the hydrodynamic regime. We investigate the trajectories of collective oscillations -- here dubbed ``weltering'' motions -- in cross-dimensional rethermalization experiments via Monte Carlo simulations, where we find stark differences from the dilute regime. These observations are interpreted within a semi-empirical theory of viscous hydrodynamics for gases confined to anisotropic harmonic potentials. The derived equations of motion provide a simple effective theory that show favorable agreement with full numerical solutions. To do so, the theory must carefully account for the size and shape of the effective volume within which the gas' behavior is hydrodynamic. Although formulated for dipolar molecules, our theoretical framework retains a flexibility to accommodate arbitrary elastic cross sections.

We consider plane wave modes in ultracold, but not quantum degenerate, dipolar Fermi gases in the hydrodynamic limit. Longitudinal waves present anisotropies in both the speed of sound and their damping, and experience a small, undulatory effect in their flow velocity. Two distinct types of shear waves appear, a "familiar" one, and another that is accompanied by nontrivial density and temperature modulations. We propose these shear modes as an experimental means to measure the viscosity coefficients, including their anisotropies.

A six-dimensional potential energy surface is constructed for the spin-polarized triplet state of CaF-CaF by ab initio calculations at the CCSD(T) level of theory, followed by Gaussian process interpolation. The potential is utilized to calculate the density of states for this bialkaline-earth-halogen system where we find the value 0.038 μK-1, implying a mean resonance spacing of 26 μK in the collision complex. This value implies an associated Rice-Ramsperger-Kassel-Marcus lifetime of 1.8 μs, thus predicting long-lived complexes in collisions at ultracold temperatures.

The presence of electric or microwave fields can modify the long-range forces between ultracold dipolar molecules in such a way as to engineer weakly bound states of molecule pairs. These so-called field-linked states [A. V. Avdeenkov and J. L. Bohn, Phys. Rev. Lett. 90, 043006 (2003).PRLTAO0031-900710.1103/PhysRevLett.90.043006; L. Lassablière and G. Quéméner, Phys. Rev. Lett. 121, 163402 (2018).PRLTAO0031-900710.1103/PhysRevLett.121.163402], in which the separation between the two bound molecules can be orders of magnitude larger than the molecules themselves, have been observed as resonances in scattering experiments [X.-Y. Chen et al., Nature (London) 614, 59 (2023).NATUAS0028-083610.1038/s41586-022-05651-8]. Here, we propose to use them as tools for the assembly of weakly bound tetramer molecules, by means of ramping an electric field, the electric-field analog of magnetoassociation in atoms. This ability would present new possibilities for constructing ultracold polyatomic molecules.

A full six-dimensional Born-Oppenheimer singlet potential energy surface is constructed for the reaction CaF + CaF $\rightarrow$ CaF$_2$ + Ca using a multireference configuration interaction (MRCI) electronic structure calculation. The {\it ab initio} data thus calculated are interpolated by Gaussian process (GP) regression. The four-body potential energy surface features one $D_{2h}$ global minimum and one $C_s$ local minimum, connected by a barrierless transition state that lends insight to the reaction mechanism. This surface is intended to be of use in understanding ultracold chemistry of CaF molecules.

We investigate the lifetimes of complexes formed in ultracold molecule collisions. Employing both transition-state-theory and an optical model approach we examine processes that can extend the lifetime of complexes beyond that predicted by Rice-Ramsperger-Kassel-Marcus theory. We focus on complexes that possess only one open channel, and find that the extreme distribution of widths for this case favors low decay rates. Thus decay from a complex into a single energetically available channel can be anomalously slow, and moreover nonexponential in time. We apply the theory to two systems of current experimental interest, RbCs and NaRb, finding qualitatively that the empirical time scales can be accounted for in the theory.

We study the application of a square perturbing lattice to the naturally forming hexagonal arrays of dipolar droplets in a dipolar Bose-Einstein condensate. We find that the application of the lattice causes spontaneous pattern formation and leads to frustration in some regimes. For certain parameters, the ground state has neither the symmetry of the intrinsic hexagonal supersolid nor the symmetry of the square lattice. These results may give another axis on which to explore dipolar Bose-Einstein condensates and to probe the nature of supersolidity.

The quantum-to-classical correspondence is often quantified in dynamics by a quantity referred to as the out-of-time-order correlator (OTOC). In chaotic systems, the OTOC is expected to grow exponentially at early time, characteristic of a Lyapunov exponent, however, exponential growth can also occur for integrable systems. Here we investigate the OTOC for realistic diatomic molecular potentials in one degree of freedom, finding that the OTOC can grow exponentially near the dissociation energy of the moelcule. Further, this dynamics is tied to the classical dynamics of the atoms at the outer classical turning point of the potential. These results should serve to guide and interpret dynamical chaos in more complex molecules.

ADVERTISEMENT RETURN TO ISSUESpecial Issue Prefac...Special Issue PrefaceNEXTCold ChemistryJohn L. BohnJohn L. BohnDepartment of Physics, University of Colorado, Boulder, Colorado 80309-0401, United StatesJILA, National Institute of Standards and Technology and the University of Colorado, Boulder, Colorado 80309-0440, United StatesMore by John L. Bohn and H. J. Lewandowski*H. J. LewandowskiDepartment of Physics, University of Colorado, Boulder, Colorado 80309-0401, United StatesJILA, National Institute of Standards and Technology and the University of Colorado, Boulder, Colorado 80309-0440, United States*E-mail: [email protected]More by H. J. Lewandowskihttps://orcid.org/0000-0002-0995-552XCite this: J. Phys. Chem. A 2023, 127, 38, 7869–7871Publication Date (Web):September 28, 2023Publication History Received24 August 2023Published online28 September 2023Published inissue 28 September 2023https://pubs.acs.org/doi/10.1021/acs.jpca.3c05726https://doi.org/10.1021/acs.jpca.3c05726introductionACS PublicationsCopyright © Published 2023 by American Chemical Society. This publication is available under these Terms of Use. Request reuse permissions This publication is free to access through this site. Learn MoreArticle Views1456Altmetric-Citations1LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail PDF (1013 KB) Get e-AlertscloseSUBJECTS:Collisions,Molecules,Probes,Scattering,Spectroscopy Get e-Alerts