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.
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.
A very recently method for classical trajectory calculations for three-body collision [Pérez-Ríos et al., J. Chem. Phys. 140, 044307 (2014)] has been applied to describe ion-neutral-neutral ternary processes for low energy collisions: 0.1 mK-10 mK. As a result, a threshold law for the three-body recombination cross section is obtained and corroborated numerically. The derived threshold law predicts the formation of weakly bound dimers, with binding energies comparable to the collision energy of the collisional partners. In this low energy range, this analysis predicts that molecular ions should dominate over molecular neutrals as the most products formed.
A very recently method for classical trajectory calculations for three-body collision [J. Pérez-Ríos, S. Ragole, J. Wang and C. H. Greene, J. Chem. Phys. {\bf 140}, 044307 (2014)] has been applied to describe ion-neutral-neutral ternary processes for low energy collisions: 0.1 mK - 10 mK. As a result, a threshold law for the three-body recombination cross section is obtained and corroborated both, experimentally and numerically. The derived threshold law predicts the formation of weakly bound dimers, with binding energies comparable to the collision energy of the collisional partners. In this low energy range, this analysis predicts that molecular ions should dominate over molecular neutrals as the most products formed.
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.
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.