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Annales de Physique

Control of chemical equilibrium through optical pumping

M. Allegrini, G. Alzetta, Paola Bicchi, Silvia Gozzini, L. Moi

Published Jan 1, 1985• 2 citations
Publisher

Abstract

Kastler has shown that the equilibrium rate between alkali dimers and atoms can be changed by optical orientation of the unpaired valence electron of the atom. Optical pumping experiments performed in Pisa which prove Kastler considerations are here recalled.
DOI
10.1051/anphys:01985001006088300

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Some years ago Kastler pointed out that the equilibrium constant for alkali metal atom dimer formation could be suppressed by polarizing the electrons so that the atoms interacted via the weak triplet potential. That basic idea has now been realized with atomic hydrogen, but using a polarization technique involving high magnetic fields and low temperature rather than optical pumping. By achieving high polarization, the gas can be stabilized at densities a few seconds over 10^18 atoms cm-3, and for minutes or hours at lower densities.
In 1950, Professor Alfred Kastler described the way in which optical fields could be used to redistribute population among the Zeeman sublevels of a given atomic state. The « optical pumping » process discovered by Kastler continues to be a research topic of current interest. With developments in laser spectroscopy, it has become important to understand the interplay of optical pumping, transit-time and collisional effects to properly interpret experimental line shapes. A brief review of the current status of the theory is given, with special emphasis on what, as yet, appear to be unresolved problems. Velocity selective optical pumping and collision-induced resonances are discussed.
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.