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.
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.
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.
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.
Inelastic collisions between dipolar molecules, assumed to be trapped in a static electric field at cold (> 10−3K) temperatures, are investigated and compared with elastic collisions. For molecules with a Λ-doublet energy-level structure, a dipole moment arises because of the existence of two nearly degenerate states of opposite parity, and the collision of two such dipoles can be solved entirely analytically in the energy range of interest. Cross sections and rate constants are found to satisfy simple, universal formulas. In contrast, for molecules in a Σ electronic ground state, the static electric field induces a dipole moment in one of three rotational sublevels. Collisions between two rotor dipoles are calculated numerically; the results scale simply with molecule mass, rotational constant, dipole moment, and field strength. It might be expected that any particles interacting only under the influence of the dipole-dipole interaction would show similar behavior; however, the most important and general result of this research is that at cold temperatures inelastic rate constants and cross sections for dipoles depend strongly upon the internal structure of the molecules. The most prominent difference between the Λ-doublet and rotor molecules is variation of the inelastic cross section with applied field strength. For Λ-doublet dipoles, cross sections decrease with increasing field strength. For rotor dipoles, cross sections increase proportionally with the square of field strength. Furthermore, the rate constants of the two types of molecules depend very differently on the angular orientations of the dipoles in the electric field.
Two elementary models of molecular structure are used to investigate inelastic collisions in cold trapped dipolar gases. A two-state model of a polar molecule (such as one with a Λ-doublet) permits analytic description of the inelastic collision process at energies considerably higher than the gap energy, predicting rate constants and cross sections given by elementary formulae. Alternatively, a three-state model of a rotor molecule in an electric field is investigated, with resultant rate constants and cross sections scaling simply with molecular mass, rotational constant, dipole moment and polarizing field strength. Semiclassical inelastic collision cross sections and rate constants are demonstrated to depend strongly on the model used, especially as regards their dependence on the polarizing field. Inelastic cross sections among doublet dipoles decrease with increasing field strength, while they increase in proportion to the square of the field strength for collisions between rotor dipoles.
We present a theoretical study of elastic and rotationally inelastic collisions of NH3 and ND3 with rare gas atoms (He, Ne, Ar, Kr, Xe) at low energy. Quantum close-coupling calculations have been performed for energies between 0.001 and 300 cm(-1). We focus on collisions in which NH3 is initially in the upper state of the inversion doublet with j = 1, k = 1, which is the most relevant in an experimental context as it can be trapped electrostatically and Stark-decelerated. We discuss the presence of resonances in the elastic and inelastic cross sections, as well as the trends in the inelastic cross sections along the rare gas series and the differences between NH3 and ND3 as a colliding partner. We also demonstrate the importance of explicitly taking into account the umbrella (inversion) motion of NH3 in order to obtain accurate scattering cross sections at low collision energy. Finally, we investigate the possibility of sympathetic cooling of ammonia using cold or ultracold rare gas atoms. We show that some systems exhibit a large ratio of elastic to inelastic cross sections in the cold regime, which is promising for sympathetic cooling experiments. The close-coupling calculations are based on previously reported ab initio potential energy surfaces for NH3-He and NH3-Ar, as well as on new, four-dimensional, potential energy surfaces for the interaction of ammonia with Ne, Kr, and Xe, which were computed using the coupled-cluster method and large basis sets. We compare the properties of the potential energy surfaces corresponding to the interaction of ammonia with the various rare gas atoms.
Ultracold molecular collision dynamics Ultracold collision dynamics are of great importance in understanding the quantum nature of chemical interactions, but achieving the ultracold regime for molecules is challenging. Traditional techniques based on alternative routes to assemble the ultracold atomic constituents are only able to produce a type of ultracold molecules that cannot probe state-selective dynamics. Using Stark deceleration and velocity map–imaging techniques, de Jongh et al. achieved the ultracold regime directly for a nitric oxide–helium system and measured the state-to-state cross sections for inelastic scattering with high precision (see the Perspective by Yang and Yang). The observed scattering resonances confirmed high sensitivity to the underlying interaction potential because only the most accurate electronic structure theory could reproduce their structure. Science , this issue p. 626 ; see also p. 582