Abstract In this work, we present a study on the role of atomic configurations in forming van der Waals molecules through three-body recombination. Fixing the angle between the two momenta associated with the Jacobi vectors, we calculate the reaction probability for a specific configuration. In this way, we elucidate the nature of the total reaction probability in reactions X + He + He$\rightarrow$XHe + He, which is essential for understanding van der Waals molecules formation in molecular beams and buffer gas cells.
Abstract In this work, we present a study on the role of atomic configurations in forming van der Waals molecules through three-body recombination. Fixing the angle between the two momenta associated with the Jacobi vectors, we calculate the reaction probability for a specific configuration. In this way, we elucidate the nature of the total reaction probability in reactions X + He + He→XHe + He, which is essential for understanding van der Waals molecules formation in molecular beams and buffer gas cells.
In this work, we show that van der Waals molecules X-RG (where RG is the rare gas atom) may be created through direct three-body recombination collisions, i.e., X + RG + RG → X-RG + RG. In particular, the three-body recombination rate at temperatures relevant for buffer gas cell experiments is calculated via a classical trajectory method in hyperspherical coordinates [Pérez-Ríos et al., J. Chem. Phys. 140, 044307 (2014)]. As a result, it is found that the formation of van der Waals molecules in buffer gas cells (1 K ≲ T ≲ 10 K) is dominated by the long-range tail (distances larger than the LeRoy radius) of the X-RG interaction. For higher temperatures, the short-range region of the potential becomes more significant. Moreover, we notice that the rate of formation of van der Walls molecules is of the same order of the magnitude independent of the chemical properties of X. As a consequence, almost any X-RG molecule may be created and observed in a buffer gas cell under proper conditions.
In this work, we show that van der Waals molecules X–RG (where RG is the rare gas atom) may be created through direct three-body recombination collisions, i.e., X + RG + RG → X–RG + RG. In particular, the three-body recombination rate at temperatures relevant for buffer gas cell experiments is calculated via a classical trajectory method in hyperspherical coordinates [Pérez-Ríos et al., J. Chem. Phys. 140, 044307 (2014)]. As a result, it is found that the formation of van der Waals molecules in buffer gas cells (1 K ≲ T ≲ 10 K) is dominated by the long-range tail (distances larger than the LeRoy radius) of the X–RG interaction. For higher temperatures, the short-range region of the potential becomes more significant. Moreover, we notice that the rate of formation of van der Walls molecules is of the same order of the magnitude independent of the chemical properties of X. As a consequence, almost any X–RG molecule may be created and observed in a buffer gas cell under proper conditions.
We study the role of pairwise long-range interactions in the formation of van der Waals molecules through direct three-body recombination processes A + B + B → AB + B, based on a classical trajectory method in hyperspherical coordinates developed in our earlier works [J. Pérez-Ríos et al., J. Chem. Phys. 140, 044307 (2014); M. Mirahmadi and J. Pérez-Ríos, J. Chem. Phys. 154, 034305 (2021)]. In particular, we find the effective long-range potential in hyperspherical coordinates with an exact expression in terms of dispersion coefficients of pairwise potentials. Exploiting this relation, we derive a classical threshold law for the total cross section and the three-body recombination rate yielding an analytical expression for the three-body recombination rate as a function of the pairwise long-range coefficients of the involved partners.
We theoretically investigate the spin structure of weakly bound diatomic van der Waals molecules formed by two identical bosonic alkali atoms. Our studies were performed using known Born-Oppenheimer potentials while developing a reduced interaction potential model. Such reduced potential models are currently a key for solving certain classes of few-body problems of atoms as they decrease the numerical burden on the computation. Although the reduced potentials are significantly shallower than actual Born-Oppenheimer potentials, they still capture the main properties of the near-threshold bound states, including their spin structure, and the scattering states over a broad range of magnetic fields. At zero magnetic field, we find that the variation in spin structure across different alkali species originates from the interplay between electronic spin exchange and hyperfine interactions. To characterize this competition we introduce a single parameter that is a function of the singlet and triplet scattering lengths, the atomic hyperfine splitting constant, and the molecular binding energy. We show that this parameter can be used to classify the spin structure of vdW molecules for each atomic species.
For a system of three identical bosons interacting via short-range forces, when two of the atoms are about to form a two-body s-wave dimer, the Efimov effect takes place leading to the formation of an infinite number of three-body (Efimov) states. The lowest Efimov state crosses the three-body break-up threshold when the s-wave two-body scattering length is $a\ensuremath{\approx}\ensuremath{-}9.73{r}_{\mathrm{vdW}}$, rvdW being the van der Waals length. This article focuses on a generalized version of this Efimov scenario, where two of the atoms are about to form a two-body d-wave dimer, resulting in strong d-wave interactions. In his paper [Phys. Rev. A 62, 050702(R) (2000)], Bo Gao predicted that for broad resonances the d-wave dimer is always formed when $a\ensuremath{\approx}0.956{r}_{\mathrm{vdW}}$. Here we find that a single universal three-body state associated with the d-wave dimer is also formed near the three-body breakup threshold at $a\ensuremath{\approx}1.09{r}_{\mathrm{vdW}}$, or alternatively a2=0.902rvdW, where a2 is the two-body d-wave scattering length. The signature of such a universal three-body state is signaled experimentally by an enhancement of the three-body recombination rate. The three-body effective potential curves that are crucial for understanding the recombination dynamics are also calculated and analyzed. An improved method to calculate the couplings, effective potential curves, and recombination rate coefficients is presented.
We show that weakly bound He-containing van der Waals molecules can be produced and magnetically trapped in buffer-gas cooling experiments, and provide a general model for the formation and dynamics of these molecules. Our analysis shows that, at typical experimental parameters, thermodynamics favors the formation of van der Waals complexes composed of a helium atom bound to most open-shell atoms and molecules, and that complex formation occurs quickly enough to ensure chemical equilibrium. For molecular pairs composed of a He atom and an S-state atom, the molecular spin is stable during formation, dissociation, and collisions, and thus these molecules can be magnetically trapped. Collisional spin relaxation is too slow to affect trap lifetimes. However, (3)He-containing complexes can change spin due to adiabatic crossings between trapped and untrapped Zeeman states, mediated by the anisotropic hyperfine interaction, causing trap loss. We provide a detailed model for Ag(3)He molecules, using ab initio calculation of Ag-He interaction potentials and spin interactions, quantum scattering theory, and direct Monte Carlo simulations to describe formation and spin relaxation in this system. The calculated rate of spin-change agrees quantitatively with experimental observations, providing indirect evidence for molecular formation in buffer-gas-cooled magnetic traps. Finally, we discuss the possibilities for spectroscopic detection of these complexes, including a calculation of expected spectra for Ag(3)He, and report on our spectroscopic search for Ag(3)He, which produced a null result.