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Physical Review A

Estimates of spin-exchange parameters for alkali-metal–noble-gas pairs

Thad G Walker

Published Nov 1, 1989• 93 citations
Publisher

Abstract

Estimates of frequency-shift enhancement factors, binary cross sections for spin exchange and spin relaxation, chemical equilibrium constants, and spin-exchange and spin-rotation interactions in van der Waals molecules are presented for alkali-metal atoms interacting with noble-gas atoms. These results are compared to experiments and are also presented for those pairs which have not been studied experimentally.

DOI
10.1103/physreva.40.4959

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Physical Review A•Jun 1, 1989•155 citations
Estimates of frequency-shift enhancement factors, binary cross sections for spin exchange and spin relaxation, chemical equilibrium constants, and spin-exchange and spin-rotation interactions in van der Waals molecules are presented for alkali-metal atoms interacting with noble-gas atoms. These results are compared to experiments and are also presented for those pairs which have not been studied experimentally.
By analyzing the measured spin-relaxation transients of 129Xe^{129}\mathrm{Xe}129Xe nuclear spins and alkali-metal-atomic spins in mixtures of alkali-metal-atom vapors, Xe gas, and larger amounts of N2{\mathrm{N}}_{2}N2​ gas, we have determined the three-body formation rates and the spin-transfer probabilities for alkali- metal--noble-gas van der Waals molecules. Three parameters, in addition to the spin quantum numbers of the alkali-metal and noble-gas nuclei, are needed to predict the spin-transfer rates. These parameters, which we have determined from experimental measurements, are x=\ensuremath{\gamma}N/\ensuremath{\alpha}, the ratio of the spin-rotation interaction \ensuremath{\gamma}N to the spin-exchange interaction \ensuremath{\alpha}; p0{p}_{0}p0​, the third-body pressure for which the molecular breakup rate ${\ensuremath{\tau}}^{\mathrm{\ensuremath{-}}1}$ is equal to the spin-rotation frequency \ensuremath{\gamma}N/h; and Z, the three-body rate constant for forming van der Waals molecules.
The spin-exchange rates due to binary collisions and due to the formation of van der Waals molecules between 83Kr^{83}\mathrm{Kr}83Kr nuclei and optically pumped rubidium-metal vapor have been determined using a technique that relies on the simultaneous observation of frequency shifts of nuclear magnetic resonance lines of noble-gas atoms and corresponding frequency shifts of electron paramagnetic resonance lines of alkali-metal atoms. In contrast, earlier studies have relied on the observation of the spin-relaxation rate of either the alkali-metal atoms or the noble-gas atoms.
A theory for calculating the spin–rotation coupling coefficient in alkali-metal–noble-gas van der Waals molecules was recently presented.1 It assumes the spin–rotation interaction in alkali-metal–noble-gas molecules to be mainly due to the spin–orbit interaction of the alkali-metal valence electron within the core of the noble gas, and predicts that the spin–rotation constant γ should depend on the spin–orbit interaction in the noble gas and be almost independent of the spin–orbit interaction of the alkali-metal atom. Experimentally, only a few of the possible pairs of the different alkali-metal atoms with different noble-gas atoms have been investigated. By measuring the sodium spin relaxation rate as a function of the helium buffer-gas pressure and the width of the sodium magnetic slowing-down curve, we report in this paper our experimentally determined value of the spin–rotation interaction constant in Na–Xe molecules γ = (1.1 ± 0.3)MHz. The measured value is nearly the same as was measured in K–Xe, Rb–Xe, and Cs–Xe.1 This result shows a reasonable agreement with the theoretical prediction.
The theory of spin exchange between optically pumped alkali-metal atoms and noble-gas nuclei is presented. Spin exchange with heavy noble gases is dominated by interactions in long-lived van der Waals molecules. The main spin interactions are assumed to be the spin-rotation interactions $\ensuremath{\gamma}\stackrel{\ensuremath{\rightarrow}}{\mathrm{N}}\ifmmode\cdot\else\textperiodcentered\fi{}\stackrel{\ensuremath{\rightarrow}}{\mathrm{S}}$ between the rotational angular momentum $\stackrel{\ensuremath{\rightarrow}}{\mathrm{N}}$ of the alkali-metal---noble-gas pair and the electron spin $\stackrel{\ensuremath{\rightarrow}}{\mathrm{S}}$ of the alkali-metal atom, and the contact hyperfine interaction $\ensuremath{\alpha}\stackrel{\ensuremath{\rightarrow}}{\mathrm{K}}\ifmmode\cdot\else\textperiodcentered\fi{}\stackrel{\ensuremath{\rightarrow}}{\mathrm{S}}$ between the nuclear spin $\stackrel{\ensuremath{\rightarrow}}{\mathrm{K}}$ of the noble-gas atom and the electron spin $\stackrel{\ensuremath{\rightarrow}}{\mathrm{S}}$. Arbitrary values for KKK and for the nuclear spin III of the alkali-metal atom are assumed. Precise formal expressions for spin transfer coefficients are given along with convenient approximations based on a perturbation expansion in powers of ${(\frac{\ensuremath{\alpha}}{\ensuremath{\gamma}N})}^{2}$, a quantity which has been shown to be small by experiment.
We report the first quantitative theoretical and experimental studies of frequency shifts of nuclear-magnetic-resonance (NMR) lines of noble-gas atoms and the corresponding frequency shifts of electron-paramagnetic-resonance (EPR) lines of alkali-metal atoms in mixtures of nuclear spin-polarized noble gases and vapors of spin-polarized alkali-metal atoms. The shifts are primarily due to the Fermi-contact hyperfine interaction. For the heavier noble gases there can be relatively large (\ensuremath{\approxeq}10%) contributions to the shifts from van der Waals molecules. The NMR frequencies of polarized 83Kr^{83}\mathrm{Kr}83Kr and 129Xe^{129}\mathrm{Xe}129Xe were measured in a vapor of spin-polarized alkali-metal atoms oriented parallel and antiparallel to the external magnetic field. The shift in the EPR frequency of the alkali-metal vapor due to the polarized noble-gas nuclei was measured simultaneously, thus providing a measurement of the absolute noble-gas nuclear polarization. The frequency shifts can be used as a convenient way to measure the absolute nuclear spin polarization of noble gases.