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The Journal of Chemical Physics

Optically pumped atomic spin orientation and the law of mass action for 2Cs⇄Cs2

J. J. Ho, Chongye Wang, Robert A. Bernheim

Published Sep 1, 1988• 7 citations
Publisher

Abstract

The effect of optically pumped atomic spin orientation on the atom–dimer equilibrium in cesium vapor has been observed. Such a shift in equilibrium was predicted over two decades ago and is due to the redistribution of spin-determined bonding and antibonding collision trajectories. Orientation of the total spin angular momentum of 6 2S1/2 ground state Cs atoms in the vapor phase was produced by optical pumping with a tunable cw dye laser. A decrease in the equilibrium molecular density resulted and was measured using laser induced fluorescence from the B 1Πu state. The shift in equilibrium is a function of the degree of atomic orientation and could be observed in the temperature range 383–421 K for cesium vapor in a glass cell which also contained a He–N2 buffer gas mixture with a composition ratio of 9:1.

DOI
10.1063/1.455013

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The effect of optically pumped atomic spin orientation on the atom–dimer equilibrium in cesium vapor has been observed. Such a shift in equilibrium was predicted over two decades ago and is due to the redistribution of spin-determined bonding and antibonding collision trajectories. Orientation of the total spin angular momentum of 6 2S1/2 ground state Cs atoms in the vapor phase was produced by optical pumping with a tunable cw dye laser. A decrease in the equilibrium molecular density resulted and was measured using laser induced fluorescence from the B 1Πu state. The shift in equilibrium is a function of the degree of atomic orientation and could be observed in the temperature range 383–421 K for cesium vapor in a glass cell which also contained a He–N2 buffer gas mixture with a composition ratio of 9:1.
A shift in the equilibrium distribution between reactants and products in the vapor phase chemical reaction 6Li+7Li=6Li 7Li is caused by the optical orientation of atomic Li spin angular momenta and is shown to be controlled by the degree of atomic orientation. The observations were carried out in a heat-pipe cell operated at 631 K and containing a He buffer gas density of 3.1×1018 cm−3. The shift is similar to that measured for the ortho molecular components in the 2 6Li=6Li2 and 2 7Li=7Li2 gas phase equilibrium reactions.
We report results of measurements and theoretical modeling of spontaneous spin polarization and associated hysteresis in an optically pumped Cs vapor. We observe hysteresis over the full range (20--450 torr) of N2{\mathrm{N}}_{2}N2​ buffer gas pressures tested, and on two hyperfine components of the D1D1D1 transition, so long as both electronic spin exchange and optical pumping of a resolved ground state hyperfine level take place faster than spin relaxation. On the $F=\stackrel{\ensuremath{\rightarrow}}{3}{F}_{e}=4$ transition, the spin angular momentum is gained from the linearly polarized pump light, while on the $\stackrel{\ensuremath{\rightarrow}}{3}3$ transition, it comes instead from the buffer gas during collisional quenching. The density-matrix theoretical model we have developed includes the effects of coherence in the excited state. It reproduces all observed features of spontaneous polarization, including hysteresis curves in quantitative agreement with the data across a broad range of experimental parameters.
An effect is demonstrated where off-resonant optical pumping is enhanced by spin-exchange collisions, which enables a high degree of spin orientation to be obtained in alkali-metal atoms. The experiment with room-temperature cesium vapor employs radio-frequency spectroscopy under conditions of the nonlinear Zeeman effect that allow the populations of the individual Zeeman sublevels to be determined. The improved efficiency of atomic orientation leads to a significant reduction of population relaxation out of the state with maximum magnetic quantum number mmm (stretched state), which is observed as a narrowing of radio-frequency resonances. Spin-exchange collisions play a crucial role in this effect although the applied atomic density $\ensuremath{\sim}101010{}^{11}$ cm${}^{\ensuremath{-}3}$ corresponds to collision rates not greater than several tens of Hz. A simplified theoretical model has been developed to reproduce the measurement results numerically.
The relaxation of atomic polarization in buffer-gas-free, paraffin-coated cesium vapor cells is studied using a variation on Franzen's technique of ``relaxation in the dark'' [Franzen, Phys. Rev. 115 850 (1959)]. In the present experiment, narrow-band, circularly polarized pump light, resonant with the Cs D2 transition, orients atoms along a longitudinal magnetic field, and time-dependent optical rotation of linearly polarized probe light is measured to determine the relaxation rates of the atomic orientation of a particular hyperfine level. The change in relaxation rates during light-induced atomic desorption (LIAD) is studied. No significant change in the spin relaxation rate during LIAD is found beyond that expected from the faster rate of spin-exchange collisions due to the increase in Cs density.
Optical orientation of reagents is one approach to achieving selectivity in a chemical reaction and has been used successfully to shift the point of equilibrium in bulk reaction mixtures of alkali-metal atoms and dimers. In addition to the continuous control of the point of equilibrium in the dimerization of sodium atoms, the control of the ortho-para nuclear spin distribution is shown here to also be a function of the degree of atomic spin orientation over a broad range. The direction of the spin conversion is para to ortho. For a mutlicomponent vapor, the optical orientation of 6Li{}^{6}\mathrm{Li}6Li in a mixture of lithium-6 and lithium-7 is shown to produce a continuous and selective control of the isotopic dimer concentrations. 6Li2{}^{6}{\mathrm{Li}}_{2}6Li2​ (para) is selectively destroyed in the presence of the other dimer species. In this way the composition of a multicomponent metal vapor system at chemical equilibrium can be manipulated. The constraint produced by the optical orientation of one of the reagents offers a technique whereby the equilibrium yield of a multicomponent bulk chemical reaction can be laser controlled in a selective and continuous fashion.