Challenges
Datasets
Workspaces
Papers
Discussions
Leaderboard
Log inSign up
Challenges
Datasets
Workspaces
Papers
Discussions
Leaderboard
Blog
Job Board
Q3AS

© 2026 Aqora Quantum S.A.S.

TermsPrivacyLegal Notice

arXiv:physics/0610219 · International Reviews in Physical Chemistry

Molecular collisions in ultracold atomic gases

Jeremy M. Hutson, Pavel Soldán

Published Jan 1, 2007• 87 citations
arXivHTMLPDF

Abstract

It has recently become possible to form molecules in ultracold gases of trapped alkali metal atoms. Once formed, the molecules may undergo elastic, inelastic and reactive collisions. Inelastic and reactive collisions are particularly important because they release kinetic energy and eject atoms and molecules from the trap. The theory needed to handle such collisions is presented and recent quantum dynamics calculations on ultracold atom–diatom collisions of spin-polarized Li + Li2, Na + Na2 and K + K2 are described. All these systems have potential energy surfaces on which barrierless atom exchange reactions can occur, and both inelastic and reactive rates are very fast (typically k inel > 10-10 cm3 s−1 in the Wigner regime).

DOI
10.1080/01442350601084562

Related papers

Quantum Dynamics of Ultracold Na+ Na2 Collisions

Pavel Soldán, Marko T. Cvitaš, Jeremy M. Hutson +2 more

Ultracold collisions between spin-polarized Na atoms and vibrationally excited ${\mathrm{N}\mathrm{a}}_{2}$ molecules are investigated theoretically, using a reactive scattering formalism (including atom exchange). Calculations are carried out on both pairwise additive and nonadditive potential energy surfaces for the quartet electronic state. The Wigner threshold laws are followed for energies below ${10}^{\ensuremath{-}5}\text{ }\mathrm{K}$. Vibrational relaxation processes dominate elastic processes for temperatures below ${10}^{\ensuremath{-}3}--{10}^{\ensuremath{-}4}\text{ }\mathrm{K}$. For temperatures below ${10}^{\ensuremath{-}5}\text{ }\mathrm{K}$, the rate coefficients for vibrational relaxation ($v=1\ensuremath{\rightarrow}0$) are $4.8\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}11}$ and $5.2\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}10}\text{ }{\mathrm{c}\mathrm{m}}^{3}\text{ }{\mathrm{s}}^{\ensuremath{-}1}$ for the additive and nonadditive potentials, respectively. The large difference emphasizes the importance of using accurate potential energy surfaces for such calculations.

arXiv:cond-mat/0205077•Physical Review Letters•Sep 18, 2002•145 citations

Inelastic Collisions and Chemical Reactions of Molecules at Ultracold Temperatures

N. Balakrishnan, Goulven Quéméner, A. Dalgarno

II. Inelastic atom -molecule collisions 2 A. Vibrational and rotational relaxation 2 1. Collisions at cold and ultracold temperatures 2 2. Shape resonances in molecular collisions 6 3. Feshbach resonances in molecular collisions 6 B. Quasi-resonant transitions 7 C. Atom -molecular ion collisions 8 III.Chemical Reactions at ultracold temperatures 9 A. Tunneling dominated reactions 9 1.Reactions at zero temperature 10 2. Feshbach resonances in reactive scattering 12 B. Barrierless reactions 14 1.Collision systems of three alkali metal atoms 14 2. Role of PES in determining ultracold reactions 16 3.Relaxation of vibrationally excited alkali metal dimers 18 4. Reactions of heteronuclear and isotopically substituted alkali-metal dimer systems 19 IV.Inelastic molecule -molecule collisions 20 A. Molecules in the ground vibrational state 20 B. Vibrationally inelastic transitions 22 V. Summary and outlook 24 References 24 I. A. Vibrational and rotational relaxation 1. Collisions at cold and ultracold temperatures

CRC Press eBooks•Jun 25, 2009•1 citation

Signatures of Non-universal Quantum Dynamics of Ultracold Chemical Reactions of Polar Alkali Dimer Molecules with Alkali Metal Atoms: Li(2S) + NaLi(a3Σ+) → Na(2S) + Li2(a3Σu+)

Masato Morita, Brian K. Kendrick, Jacek A. Kłos +3 more

Ultracold chemical reactions of weakly bound triplet-state alkali metal dimer molecules have recently attracted much experimental interest. We perform rigorous quantum scattering calculations with a new ab initio potential energy surface to explore the chemical reaction of spin-polarized NaLi( a 3 Σ + ) and Li( 2 S) to form Li 2 ( a 3 Σ u + ) and Na( 2 S). The reaction is exothermic and proceeds readily at ultralow temperatures. Significantly, we observe strong sensitivity of the total reaction rate to small variations of the three-body part of the Li 2 Na interaction at short range, which we attribute to a relatively small number of open Li 2 ( a 3 Σ u + ) product channels populated in the reaction. This provides the first signature of highly non-universal dynamics seen in rigorous quantum reactive scattering calculations of an ultracold exothermic insertion reaction involving a polar alkali dimer molecule, opening up the possibility of probing microscopic interactions in atom+molecule collision complexes via ultracold reactive scattering experiments.

arXiv:2301.08208•The Journal of Physical Chemistry Letters•Mar 31, 2023•12 citations

Interactions and dynamics in Li+Li2 ultracold collisions

Marko T. Cvitaš, Pavel Soldán, Jeremy M. Hutson +2 more

A potential energy surface for the lowest quartet electronic state ((4)A(')) of lithium trimer is developed and used to study spin-polarized Li+Li(2) collisions at ultralow kinetic energies. The potential energy surface allows barrierless atom exchange reactions. Elastic and inelastic cross sections are calculated for collisions involving a variety of rovibrational states of Li(2). Inelastic collisions are responsible for trap loss in molecule production experiments. Isotope effects and the sensitivity of the results to details of the potential energy surface are investigated. It is found that for vibrationally excited states, the cross sections are only quite weakly dependent on details of the potential energy surface.

arXiv:physics/0703136•The Journal of Chemical Physics•Aug 20, 2007•71 citations

Interactions and collisions of cold molecules: lithium + lithium dimer

Marko T. Cvitaš

There is at present great interest in the properties of ultracold molecules. Molecules are created in traps in excited rovibrational states and any vibrational relaxation results in the trap loss. This thesis provides a theoretical study of interactions and collisions in the spin-polarized lithium -b lithium dimer system at ultralow energies. Potential energy surface of the electronic quartet ground state of lithium trimer is generated ab initio using the CCSD(T) method and represented by an IMLS/Shepard fit. Long-range nonadditive interactions are modelled using a symmetric global form with coefficients taken from a fit to the atom-molecule dispersion coefficients. The surface allows barrierless atom-exchange reactions. It has a global minimum of ≈ 4000 cm(^-1) at equilateral geometries with r(_e) = 3.1 Å. The nonadditive interactions are very strong near equilibrium. They increase the well depth by a factor of 4 and reduce the interatomic distance by ≈ 1 Å. Another surface of À symmetry in C(_s) meets the ground state surface at linear geometries at short range. Part of the seam, near D(_ooh) geometries, is in an energetically accessible region for cold collisions. Inside the seam, the lowest À surface correlates with (^4)II rather than (^4)Σ state. Inelastic and reactive collisions are investigated using a quantum mechanical coupled channel method in hyperspherical coordinates. Bosonic and fermionic systems in the spin-stretched states are considered. The inelastic rate coefficients from the rovibrationally excited states of dimer at ultralow collision energies are large, often above 10-(^-10) cm(^3)s(^-1) The elastic cross sections are ≈ 3 orders of magnitude lower at 1 nK. Atom-molecule mixtures, at the densities found in Bose-Einstein condensates of alkali metal atoms that were recently produced, would last only a fraction of a second. Classical Langevin model describes semi-quantitatively the energy dependence of inelastic cross sections above ≈ 50 mK. No systematic differences between the bosonic and fermionic systems were found. Sensitivity of the results on potential was investigated. Reactions in isotopic mixtures of lithium may be exothermic even from the molecular ground state. The reactive rate coefficients are 1 - 2 orders of magnitude smaller than those in systems involving an initially vibrationally excited dimer.

•Jan 1, 2004•0 citations

Scattering of ultracold molecules in the highly resonant regime

Michael Mayle, Goulven Quéméner, Brandon Ruzic +1 more

Compared to purely atomic collisions, ultracold molecular collisions potentially support a much larger number of Fano-Feshbach resonances due to the enormous number of rovibrational states available. In fact, for alkali-metal dimers we find that the resulting density of resonances cannot be resolved at all, even on the sub-$\ensuremath{\mu}$K temperature scale of ultracold experiments. As a result, all observables become averaged over many resonances and can effectively be described by simpler, nonresonant scattering calculations. Two particular examples are discussed: nonchemically reactive RbCs and chemically reactive KRb. In the former case, the formation of a long-lived collision complex may lead to the ejection of molecules from a trap. In the latter case, chemical reactions broaden the resonances so much that they become unobservable.

Physical Review A•Jan 24, 2013•206 citations
It has recently become possible to form molecules in ultracold gases of trapped alkali metal atoms. Once formed, the molecules may undergo elastic, inelastic and reactive collisions. Inelastic and reactive collisions are particularly important because they release kinetic energy and eject atoms and molecules from the trap. The theory needed to handle such collisions is presented and recent quantum dynamics calculations on ultracold atom–diatom collisions of spin-polarized Li + Li2, Na + Na2 and K + K2 are described. All these systems have potential energy surfaces on which barrierless atom exchange reactions can occur, and both inelastic and reactive rates are very fast (typically k inel > 10-10 cm3 s−1 in the Wigner regime).
Ultracold collisions between spin-polarized Na atoms and vibrationally excited Na2{\mathrm{N}\mathrm{a}}_{2}Na2​ molecules are investigated theoretically, using a reactive scattering formalism (including atom exchange). Calculations are carried out on both pairwise additive and nonadditive potential energy surfaces for the quartet electronic state. The Wigner threshold laws are followed for energies below ${10}^{\ensuremath{-}5}\text{ }\mathrm{K}$. Vibrational relaxation processes dominate elastic processes for temperatures below ${10}^{\ensuremath{-}3}--{10}^{\ensuremath{-}4}\text{ }\mathrm{K}$. For temperatures below ${10}^{\ensuremath{-}5}\text{ }\mathrm{K}$, the rate coefficients for vibrational relaxation ($v=1\ensuremath{\rightarrow}0$) are $4.8\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}11}$ and $5.2\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}10}\text{ }{\mathrm{c}\mathrm{m}}^{3}\text{ }{\mathrm{s}}^{\ensuremath{-}1}$ for the additive and nonadditive potentials, respectively. The large difference emphasizes the importance of using accurate potential energy surfaces for such calculations.
II. Inelastic atom -molecule collisions 2 A. Vibrational and rotational relaxation 2 1. Collisions at cold and ultracold temperatures 2 2. Shape resonances in molecular collisions 6 3. Feshbach resonances in molecular collisions 6 B. Quasi-resonant transitions 7 C. Atom -molecular ion collisions 8 III.Chemical Reactions at ultracold temperatures 9 A. Tunneling dominated reactions 9 1.Reactions at zero temperature 10 2. Feshbach resonances in reactive scattering 12 B. Barrierless reactions 14 1.Collision systems of three alkali metal atoms 14 2. Role of PES in determining ultracold reactions 16 3.Relaxation of vibrationally excited alkali metal dimers 18 4. Reactions of heteronuclear and isotopically substituted alkali-metal dimer systems 19 IV.Inelastic molecule -molecule collisions 20 A. Molecules in the ground vibrational state 20 B. Vibrationally inelastic transitions 22 V. Summary and outlook 24 References 24 I. A. Vibrational and rotational relaxation 1. Collisions at cold and ultracold temperatures
Ultracold chemical reactions of weakly bound triplet-state alkali metal dimer molecules have recently attracted much experimental interest. We perform rigorous quantum scattering calculations with a new ab initio potential energy surface to explore the chemical reaction of spin-polarized NaLi( a 3 Σ + ) and Li( 2 S) to form Li 2 ( a 3 Σ u + ) and Na( 2 S). The reaction is exothermic and proceeds readily at ultralow temperatures. Significantly, we observe strong sensitivity of the total reaction rate to small variations of the three-body part of the Li 2 Na interaction at short range, which we attribute to a relatively small number of open Li 2 ( a 3 Σ u + ) product channels populated in the reaction. This provides the first signature of highly non-universal dynamics seen in rigorous quantum reactive scattering calculations of an ultracold exothermic insertion reaction involving a polar alkali dimer molecule, opening up the possibility of probing microscopic interactions in atom+molecule collision complexes via ultracold reactive scattering experiments.
A potential energy surface for the lowest quartet electronic state ((4)A(')) of lithium trimer is developed and used to study spin-polarized Li+Li(2) collisions at ultralow kinetic energies. The potential energy surface allows barrierless atom exchange reactions. Elastic and inelastic cross sections are calculated for collisions involving a variety of rovibrational states of Li(2). Inelastic collisions are responsible for trap loss in molecule production experiments. Isotope effects and the sensitivity of the results to details of the potential energy surface are investigated. It is found that for vibrationally excited states, the cross sections are only quite weakly dependent on details of the potential energy surface.
There is at present great interest in the properties of ultracold molecules. Molecules are created in traps in excited rovibrational states and any vibrational relaxation results in the trap loss. This thesis provides a theoretical study of interactions and collisions in the spin-polarized lithium -b lithium dimer system at ultralow energies. Potential energy surface of the electronic quartet ground state of lithium trimer is generated ab initio using the CCSD(T) method and represented by an IMLS/Shepard fit. Long-range nonadditive interactions are modelled using a symmetric global form with coefficients taken from a fit to the atom-molecule dispersion coefficients. The surface allows barrierless atom-exchange reactions. It has a global minimum of ≈ 4000 cm(^-1) at equilateral geometries with r(_e) = 3.1 Å. The nonadditive interactions are very strong near equilibrium. They increase the well depth by a factor of 4 and reduce the interatomic distance by ≈ 1 Å. Another surface of À symmetry in C(_s) meets the ground state surface at linear geometries at short range. Part of the seam, near D(_ooh) geometries, is in an energetically accessible region for cold collisions. Inside the seam, the lowest À surface correlates with (^4)II rather than (^4)Σ state. Inelastic and reactive collisions are investigated using a quantum mechanical coupled channel method in hyperspherical coordinates. Bosonic and fermionic systems in the spin-stretched states are considered. The inelastic rate coefficients from the rovibrationally excited states of dimer at ultralow collision energies are large, often above 10-(^-10) cm(^3)s(^-1) The elastic cross sections are ≈ 3 orders of magnitude lower at 1 nK. Atom-molecule mixtures, at the densities found in Bose-Einstein condensates of alkali metal atoms that were recently produced, would last only a fraction of a second. Classical Langevin model describes semi-quantitatively the energy dependence of inelastic cross sections above ≈ 50 mK. No systematic differences between the bosonic and fermionic systems were found. Sensitivity of the results on potential was investigated. Reactions in isotopic mixtures of lithium may be exothermic even from the molecular ground state. The reactive rate coefficients are 1 - 2 orders of magnitude smaller than those in systems involving an initially vibrationally excited dimer.
Compared to purely atomic collisions, ultracold molecular collisions potentially support a much larger number of Fano-Feshbach resonances due to the enormous number of rovibrational states available. In fact, for alkali-metal dimers we find that the resulting density of resonances cannot be resolved at all, even on the sub-$\ensuremath{\mu}$K temperature scale of ultracold experiments. As a result, all observables become averaged over many resonances and can effectively be described by simpler, nonresonant scattering calculations. Two particular examples are discussed: nonchemically reactive RbCs and chemically reactive KRb. In the former case, the formation of a long-lived collision complex may lead to the ejection of molecules from a trap. In the latter case, chemical reactions broaden the resonances so much that they become unobservable.