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

Physical Review

Evidence for Rb-Rare-Gas Molecules from the Relaxation of Polarized Rb Atoms in a Rare Gas. Theory

Claude C. Bouchiat, Marie-Anne Bouchiat, Lionel Pottier

Published May 5, 1969• 88 citations
Publisher

Abstract

Relaxation experiments performed on optically polarized Rb atoms in a rare gas have been previously reported; their detailed interpretation is given below. It is shown that the relaxation governed by the spin-orbit interaction is strongly affected by the formation of chemically unstable Rb-Kr molecules bound by van der Waals forces. Two processes of molecule formation are analyzed: binary resonant collisions leading to metastable states and three-body collisions producing actual bound states. A relaxation model valid for any disorientation probability per single Rb-Kr interaction is developed. Aside from clear evidence for the existence of alkali-rare-gas molecules, the success of the theoretical interpretation of the relaxation experiments yields the equilibrium constant $\mathcal{K}=1.7\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}22}$ ${\mathrm{cm}}^{3}$/molecule for the reaction Rb+Kr \ensuremath{\rightleftharpoons} Rb-Kr at 300\ifmmode^\circ\else\textdegree\fi{}K, the average lifetime of a Rb-Kr molecule in the gas phase, $\ensuremath{\tau}=0.65\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}7}$ sec, at a krypton pressure of one Torr, and the average spin-orbit coupling constant in a Rb-Kr molecule, $\overline{\ensuremath{\gamma}}{h}^{\ensuremath{-}1}=0.63$ MHz. It is also shown that the spin-orbit potential is predominantly short-range.

DOI
10.1103/physrev.181.144

Related papers

Evidence for Rb-Rare-Gas Molecules from the Relaxation of Polarized Rb Atoms in a Rare Gas. Experimental Results

Marie-Anne Bouchiat, J. Brossel, Lionel Pottier

Relaxation experiments have been performed between 0–200 G on optically polarized Rb atoms in argon, krypton or xenon, at pressures ranging from 0.1 to 20 torr. They clearly show the existence of Rb–Ar, Rb–Kr and Rb–Xe molecules of low binding energy (smaller than kT). Molecular parameters such as lifetime, spin-orbit coupling constant, formation rate, constant of mass action, etc., are measured, or evaluated when they cannot be directly measured. Experimental values of the diffusion coefficient of Rb in the gas (except xenon) and of the disorientation cross sections by usual binary collisions are also obtained.

The Journal of Chemical Physics•Apr 1, 1972•120 citations

Alkali-Rare-Gas van der Waals Molecules and Ground-State Relaxation Processes in Optical Pumping

Claude C. Bouchiat, Marie-Anne Bouchiat

Relaxation experiments performed on alkali atoms polarized in their ground state by optical pumping in the presence of a rare gas have been previously reported and interpreted. It was shown that the relaxation governed by the spin-orbit interaction is strongly affected by the formation of chemically unstable Rb-Kr molecules bound by van der Waals forces. The previous theoretical analysis, restricted to the longitudinal relaxation, is extended here to relaxation processes involving the transverse components of the electronic polarization and hyperfine "coherences" (elements of the density matrix between different hyperfine states). The effects resulting from the action of a rf field are also examined. The main results of this work, among others, are (a) the prediction of a Zeeman transition-line pressure shift, in some circumstances larger by several orders of magnitude than the one calculated by Herman, and having a very peculiar variation with the rare-gas pressure; (b) a quantitative explanation of the anomalous pressure dependence of the hyperfine transition linewidth discovered by Bender and Cohen; (c) a proposal of a method of detection of rf transitions between states of the alkali---rare-gas molecules by their effect on the relaxation process.

Physical Review A•Oct 1, 1970•23 citations

Spin relaxation of rubidium atoms in sudden and quasimolecular collisions with light-noble-gas atoms

F. A. Franz, C. H. Volk

Spin relaxation of optically pumped ${\mathrm{Rb}}^{85}$ and ${\mathrm{Rb}}^{87}$ atoms colliding with light-noble-gas atoms is shown to be strongly influenced by an anomalous relaxation process which we attribute to the formation and destruction of bound and quasibound Van der Waals molecules. The anomalous relaxation rate has been measured and analyzed in Ne, complementing an earlier study in He. Relative rates of formation of complexes in two- and three-body collisions have been determined. The correlation time for the quasimolecular interaction in Rb-Ne has been found to be 6.7 \ifmmode\times\else\texttimes\fi{} ${10}^{\ensuremath{-}10}$ ${p}^{\ensuremath{-}1}$ sec, where $p$ is the Ne pressure in Torr. Nuclear-spin-independent cross sections for the relaxation of $〈{S}_{z}〉$ in sudden binary collisions of Rb atoms with noble-gas atoms have been measured to be (units of ${10}^{\ensuremath{-}24}$ ${\mathrm{cm}}^{2}$: $\ensuremath{\sigma}(\mathrm{Rb}\ensuremath{-}\mathrm{He})=3.1$ $\ensuremath{\sigma}(\mathrm{Rb}\ensuremath{-}\mathrm{Ne})=19$ $\ensuremath{\sigma}(\mathrm{Rb}\ensuremath{-}\mathrm{Ar})=630$ $\ensuremath{\sigma}(\mathrm{Rb}\ensuremath{-}{\mathrm{N}}_{2})=83$. Relaxation in sudden binary collisions is shown to follow the theoretically expected nuclear spin dynamics: two relaxation rates in the ratios 8:1 for ${\mathrm{Rb}}^{87}$ and 18:1 for ${\mathrm{Rb}}^{85}$ have been measured. Diffusion coefficients of Rb in the various buffer gases have been measured to be (units of ${\mathrm{cm}}^{2}$/ sec, at 305\ifmmode^\circ\else\textdegree\fi{}K): ${D}_{0}(\mathrm{Rb}\ensuremath{-}\mathrm{He})=0.42$, ${D}_{0}(\mathrm{Rb}\ensuremath{-}\mathrm{Ne})=0.235$, ${D}_{0}(\mathrm{Rb}\ensuremath{-}\mathrm{Ar})=0.16$, ${D}_{0}(\mathrm{Rb}\ensuremath{-}{\mathrm{N}}_{2})=0.16$. Nuclear-spin-independent cross sections for the relaxation of $〈{J}_{z}〉$ in the $5^{2}P_{\frac{1}{2}}$ state of Rb have been measured to be 3.4 \ifmmode\times\else\texttimes\fi{} ${10}^{\ensuremath{-}16}$ ${\mathrm{cm}}^{2}$ for Rb-He, and 5.9 \ifmmode\times\else\texttimes\fi{} ${10}^{\ensuremath{-}16}$ ${\mathrm{cm}}^{2}$ for Rb-Ne. Anomalies, disagreements, and puzzles occurring in earlier measurements of ground-state relaxation in Rb are shown to be largely resolved when considered in the light of the new results.

Physical Review A•Nov 1, 1976•55 citations

Rubidium Spin Relaxation in the Rare Gases Under Ultraclean Conditions

F. A. Franz

The spin relaxation of optically pumped rubidium vapor induced by rubidium-rare-gas atomic collisions has been investigated in an ultraclean environment. The experiment was performed under conditions such that the partial pressure of nonrare-gas impurities was less than 1\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}8}$ Torr, and that the time between Rb-Rb spin exchange collisions was short compared to the spin relaxation time. The cross sections (in ${\mathrm{cm}}^{2}$) for disorientation of rubidium were found to be: He, 3.3\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}25}$; Ne, 3.3\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}24}$; Ar, 1.1\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}22}$; Kr, 7.3\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}21}$; Xe, 1.3\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}19}$. The fact that these cross sections are considerably smaller than previously reported values is attributed primarily to the low degree of impurity contamination in the present work. When compared with already existing values for cesium and sodium, the disorientation cross sections of these three alkali metals are seen to have a remarkably similar dependence on buffer-gas atomic number. The new experimental values are also compared with recent theoretical calculations.

Physical Review•Aug 2, 1965•33 citations

RF experiments on Rb-rare-gas Van der Waals molecules

Marie-Anne Bouchiat, Lionel Pottier

We have detected the action of a rf field on Rb-Kr and Rb-Ar molecules by optical pumping techniques. At a low rare-gas pressure, the experiment can be compared with one of magnetic resonance performed on these molecules. It provides significant information about the dependence of the spin-orbit interaction strength on the rotation-vibrational state of the molecule. Preliminary experimental results are in excellent quantitative agreement with the theory.

Journal de physique•Jan 1, 1972•17 citations

Interpretation of Experimental Results on the Relaxation of Optically Pumped Rb in Collisions with Kr Atoms

Marie-Anne Bouchiat, J. Brossel, L. Pottier

A theoretical analysis of experimental results on the relaxation induced by Rb-Kr collisions reveals the existence of two very different correlation times. The shorter, of the order of ${10}^{\ensuremath{-}12}$ sec, is a kinetic collision time; the longer, ${10}^{\ensuremath{-}8}$ sec, reflects the presence of metastable states associated with resonances in Rb-Kr scattering, or of actual Rb-Kr bound states due to three-body collisions.

Physical Review Letters•Oct 9, 1967•30 citations
Relaxation experiments performed on optically polarized Rb atoms in a rare gas have been previously reported; their detailed interpretation is given below. It is shown that the relaxation governed by the spin-orbit interaction is strongly affected by the formation of chemically unstable Rb-Kr molecules bound by van der Waals forces. Two processes of molecule formation are analyzed: binary resonant collisions leading to metastable states and three-body collisions producing actual bound states. A relaxation model valid for any disorientation probability per single Rb-Kr interaction is developed. Aside from clear evidence for the existence of alkali-rare-gas molecules, the success of the theoretical interpretation of the relaxation experiments yields the equilibrium constant K=1.7\ifmmode×\else\texttimes\fi10\ensuremath−22\mathcal{K}=1.7\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}22}K=1.7\ifmmode×\else\texttimes\fi10\ensuremath−22 cm3{\mathrm{cm}}^{3}cm3/molecule for the reaction Rb+Kr \ensuremath{\rightleftharpoons} Rb-Kr at 300\ifmmode^\circ\else\textdegree\fi{}K, the average lifetime of a Rb-Kr molecule in the gas phase, \ensuremathτ=0.65\ifmmode×\else\texttimes\fi10\ensuremath−7\ensuremath{\tau}=0.65\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}7}\ensuremathτ=0.65\ifmmode×\else\texttimes\fi10\ensuremath−7 sec, at a krypton pressure of one Torr, and the average spin-orbit coupling constant in a Rb-Kr molecule, \ensuremathγ‾h\ensuremath−1=0.63\overline{\ensuremath{\gamma}}{h}^{\ensuremath{-}1}=0.63\ensuremathγ​h\ensuremath−1=0.63 MHz. It is also shown that the spin-orbit potential is predominantly short-range.
Relaxation experiments have been performed between 0–200 G on optically polarized Rb atoms in argon, krypton or xenon, at pressures ranging from 0.1 to 20 torr. They clearly show the existence of Rb–Ar, Rb–Kr and Rb–Xe molecules of low binding energy (smaller than kT). Molecular parameters such as lifetime, spin-orbit coupling constant, formation rate, constant of mass action, etc., are measured, or evaluated when they cannot be directly measured. Experimental values of the diffusion coefficient of Rb in the gas (except xenon) and of the disorientation cross sections by usual binary collisions are also obtained.
Relaxation experiments performed on alkali atoms polarized in their ground state by optical pumping in the presence of a rare gas have been previously reported and interpreted. It was shown that the relaxation governed by the spin-orbit interaction is strongly affected by the formation of chemically unstable Rb-Kr molecules bound by van der Waals forces. The previous theoretical analysis, restricted to the longitudinal relaxation, is extended here to relaxation processes involving the transverse components of the electronic polarization and hyperfine "coherences" (elements of the density matrix between different hyperfine states). The effects resulting from the action of a rf field are also examined. The main results of this work, among others, are (a) the prediction of a Zeeman transition-line pressure shift, in some circumstances larger by several orders of magnitude than the one calculated by Herman, and having a very peculiar variation with the rare-gas pressure; (b) a quantitative explanation of the anomalous pressure dependence of the hyperfine transition linewidth discovered by Bender and Cohen; (c) a proposal of a method of detection of rf transitions between states of the alkali---rare-gas molecules by their effect on the relaxation process.
Spin relaxation of optically pumped Rb85{\mathrm{Rb}}^{85}Rb85 and Rb87{\mathrm{Rb}}^{87}Rb87 atoms colliding with light-noble-gas atoms is shown to be strongly influenced by an anomalous relaxation process which we attribute to the formation and destruction of bound and quasibound Van der Waals molecules. The anomalous relaxation rate has been measured and analyzed in Ne, complementing an earlier study in He. Relative rates of formation of complexes in two- and three-body collisions have been determined. The correlation time for the quasimolecular interaction in Rb-Ne has been found to be 6.7 \ifmmode\times\else\texttimes\fi{} ${10}^{\ensuremath{-}10}$ ${p}^{\ensuremath{-}1}$ sec, where ppp is the Ne pressure in Torr. Nuclear-spin-independent cross sections for the relaxation of 〈Sz〉〈{S}_{z}〉〈Sz​〉 in sudden binary collisions of Rb atoms with noble-gas atoms have been measured to be (units of ${10}^{\ensuremath{-}24}$ cm2{\mathrm{cm}}^{2}cm2: $\ensuremath{\sigma}(\mathrm{Rb}\ensuremath{-}\mathrm{He})=3.1$ $\ensuremath{\sigma}(\mathrm{Rb}\ensuremath{-}\mathrm{Ne})=19$ $\ensuremath{\sigma}(\mathrm{Rb}\ensuremath{-}\mathrm{Ar})=630$ $\ensuremath{\sigma}(\mathrm{Rb}\ensuremath{-}{\mathrm{N}}_{2})=83$. Relaxation in sudden binary collisions is shown to follow the theoretically expected nuclear spin dynamics: two relaxation rates in the ratios 8:1 for Rb87{\mathrm{Rb}}^{87}Rb87 and 18:1 for Rb85{\mathrm{Rb}}^{85}Rb85 have been measured. Diffusion coefficients of Rb in the various buffer gases have been measured to be (units of cm2{\mathrm{cm}}^{2}cm2/ sec, at 305\ifmmode^\circ\else\textdegree\fi{}K): ${D}_{0}(\mathrm{Rb}\ensuremath{-}\mathrm{He})=0.42$, ${D}_{0}(\mathrm{Rb}\ensuremath{-}\mathrm{Ne})=0.235$, ${D}_{0}(\mathrm{Rb}\ensuremath{-}\mathrm{Ar})=0.16$, ${D}_{0}(\mathrm{Rb}\ensuremath{-}{\mathrm{N}}_{2})=0.16$. Nuclear-spin-independent cross sections for the relaxation of 〈Jz〉〈{J}_{z}〉〈Jz​〉 in the 52P125^{2}P_{\frac{1}{2}}52P21​​ state of Rb have been measured to be 3.4 \ifmmode\times\else\texttimes\fi{} ${10}^{\ensuremath{-}16}$ cm2{\mathrm{cm}}^{2}cm2 for Rb-He, and 5.9 \ifmmode\times\else\texttimes\fi{} ${10}^{\ensuremath{-}16}$ cm2{\mathrm{cm}}^{2}cm2 for Rb-Ne. Anomalies, disagreements, and puzzles occurring in earlier measurements of ground-state relaxation in Rb are shown to be largely resolved when considered in the light of the new results.
The spin relaxation of optically pumped rubidium vapor induced by rubidium-rare-gas atomic collisions has been investigated in an ultraclean environment. The experiment was performed under conditions such that the partial pressure of nonrare-gas impurities was less than 1\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}8}$ Torr, and that the time between Rb-Rb spin exchange collisions was short compared to the spin relaxation time. The cross sections (in cm2{\mathrm{cm}}^{2}cm2) for disorientation of rubidium were found to be: He, 3.3\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}25}$; Ne, 3.3\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}24}$; Ar, 1.1\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}22}$; Kr, 7.3\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}21}$; Xe, 1.3\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}19}$. The fact that these cross sections are considerably smaller than previously reported values is attributed primarily to the low degree of impurity contamination in the present work. When compared with already existing values for cesium and sodium, the disorientation cross sections of these three alkali metals are seen to have a remarkably similar dependence on buffer-gas atomic number. The new experimental values are also compared with recent theoretical calculations.