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arXiv:2604.12063 · Physical Review A

Limits of statistical models of ultracold complex lifetimes

Kevin B. Xu, John L. Bohn

Published Sep 9, 2026• 0 citations
arXivHTMLPDF

Abstract

The puzzle of "sticky collisions," in which molecular collision complexes exhibit unexpectedly long lifetimes, remains an unresolved mystery. A central challenge to solving this mystery is that traditional close-coupling calculations remain limited by the vast computational cost needed to take into account all the degrees of freedom involved in the collision. In this work, we propose a statistical model designed to simulate the result of full close-coupling calculations, with the goal of collecting statistics about reasonable lifetimes of collision complexes. To do so, we numerically sample resonances using random matrix theory and utilize results from quantum defect theory to calculate scattering properties and lifetimes. We find that in the limit of dense resonances, our theory agrees well with the Rice-Ramsperger-Kassel-Markus (RRKM) prediction, whereas in the limit of sparse resonances, the physics is governed by threshold behavior rather than resonant effects. By comparing these predictions to experimental results in two limits, we argue that close-coupling calculations alone may be insufficient to resolve the issue of long lifetimes.

DOI
10.1103/q4fv-8nc4

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The puzzle of "sticky collisions," in which molecular collision complexes exhibit unexpectedly long lifetimes, remains an unresolved mystery. A central challenge to solving this mystery is that traditional close-coupling calculations remain limited by the vast computational cost needed to take into account all the degrees of freedom involved in the collision. In this work, we propose a statistical model designed to simulate the result of full close-coupling calculations, with the goal of collecting statistics about reasonable lifetimes of collision complexes. To do so, we numerically sample resonances using random matrix theory and utilize results from quantum defect theory to calculate scattering properties and lifetimes. We find that in the limit of dense resonances, our theory agrees well with the Rice-Ramsperger-Kassel-Markus (RRKM) prediction, whereas in the limit of sparse resonances, the physics is governed by threshold behavior rather than resonant effects. By comparing these predictions to experimental results in two limits, we argue that close-coupling calculations alone may be insufficient to resolve the issue of long lifetimes.
Collisional complexes, which are formed as intermediate states in molecular collisions, are typically short-lived and decay within picoseconds. However, in ultracold collisions involving bialkali molecules, complexes can live for milliseconds, completely changing the collision dynamics. This can lead to unexpected two-body loss in samples of nonreactive molecules. During the past decade, such "sticky" collisions have been a major hindrance in the preparation of dense and stable molecular samples, especially in the quantum-degenerate regime. Currently, the behavior of the complexes is not fully understood. For example, in some cases, their lifetime has been measured to be many orders of magnitude longer than recent models predict. This is not only an intriguing problem in itself but also practically relevant, since understanding molecular complexes may help to mitigate their detrimental effects. Here, we review the recent experimental and theoretical progress in this field. We treat the case of molecule-molecule as well as molecule-atom collisions.
We investigate the lifetimes of complexes formed in ultracold molecule collisions. Employing both transition-state theory and a non-Hermitian microscopic model, we examine processes that can extend the lifetime of complexes beyond that predicted by Rice-Ramsperger-Kassel-Marcus (RRKM) 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, even orders of magnitude slower than the RRKM rate, and moreover the decay may be nonexponential in time.
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 consider losses in collisions of ultracold molecules described by a simple statistical short-range model that explicitly accounts for the limited lifetime of classically chaotic collision complexes. This confirms that thermally sampling many isolated resonances leads to a loss cross section equal to the elastic cross section derived by Mayle et al. [Phys. Rev. A 85, 062712 (2012)] and this makes precise the conditions under which this is the case. Surprisingly, we find that the loss is nonuniversal. We also consider the case that loss broadens the short-range resonances to the point that they become overlapping. The overlapping resonances can be treated statistically even if the resonances are sparse compared to kBT{k}_{B}TkB​T, which may be the case for many molecules. The overlap results in Ericson fluctuations which yield a nonuniversal short-range boundary condition that is independent of energy over a range much wider than is sampled thermally. Deviations of experimental loss rates from the present theory beyond statistical fluctuations and the dependence on a background phase shift are interpreted as nonchaotic dynamics of short-range collision complexes.
Lifetimes of complexes formed during ultracold collisions are of current experimental interest as a possible cause of trap loss in ultracold gases of alkali-metal dimers. Microsecond lifetimes for complexes formed during ultracold elastic collisions of K2{\mathrm{K}}_{2}K2​ with Rb are reported, from numerically exact quantum-scattering calculations. Thermally averaged lifetimes are compared with those calculated using a simple density-of-states approach, which are shown to be reasonable. This validates the density-of-states approach and suggests that the formation of long-lived complexes is indeed the cause of observed experimental trap loss in ultracold alkali-metal-dimer systems. Long-lived complexes correspond to narrow scattering resonances which we examine for the statistical signatures of quantum chaos, finding that the positions and widths of the resonances are in good agreement with the Wigner-Dyson and Porter-Thomas distributions, respectively.
Compared to purely atomic collisions, ultracold collisions involving molecules have the potential to support a much larger number of Fano-Feshbach resonances due to the huge amount of ro-vibrational states available. In order to handle such ultracold atom-molecule collisions, we formulate a theory that incorporates the ro-vibrational Fano-Feshbach resonances in a statistical manner while treating the physics of the long-range scattering, which is sensitive to such things as hyperfine states, collision energy, and any applied electromagnetic fields, exactly within multichannel quantum defect theory. Uniting these two techniques, we can assess the influence of highly resonant scattering in the threshold regime, and in particular its dependence on the hyperfine state selected for the collision. This allows us to explore the onset of Ericson fluctuations in the regime of overlapping resonances, which are well known in nuclear physics but completely unexplored in the ultracold domain.