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Conference on Lasers and Electro-Optics

Relative yields and cross sections for atomic thallium slates produced in photodissociation of thallium halide vapors

D. A. Scott, James A. Piper

Published Jan 1, 1985• 0 citations
Publisher

Abstract

The UV absorption spectra of thallium halide vapors consist of a series of peaks corresponding to various photodissociation channels leading to the formation of different states of the product atoms.1 There has been renewed interest in determining the yields of different states of the metal atom produced by photodissociation of the thallium halides, particularly with a view to establishing conditions for selective production of metastable excited states for anti-Stokes Raman shitting2 and other purposes.

DOI
10.1364/cleo.1985.wi5

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The Journal of Chemical Physics•Dec 1, 1986•1 citation
The UV absorption spectra of thallium halide vapors consist of a series of peaks corresponding to various photodissociation channels leading to the formation of different states of the product atoms.1 There has been renewed interest in determining the yields of different states of the metal atom produced by photodissociation of the thallium halides, particularly with a view to establishing conditions for selective production of metastable excited states for anti-Stokes Raman shitting2 and other purposes.
The cross sections for production of 62P1/2 and 62P3/2 ground and metastable atomic thallium states via UV dissociation of the thallium halides TlCl, TlBr, and TlI have been measured at wavelengths 193, 222, 249, 308, and 353 nm using time-resolved atomic resonance absorption spectroscopy. The measured cross sections, which were independent of halide densities up to densities ∼1017 cm−3, were found to represent only 10% to 36% of the total UV absorption cross section at the appropriate wavelength.
Decay rates of the 6 2P3/2 metastable and 6 2P1/2 ground state atomic thallium densities produced in UV photodissociation (at λ193, 222, 249, 308, and 353 nm) of TlI, TlBr, and TlCl molecular vapors have been measured for vapor densities from 1013 to 1017 cm−3. Dominant relaxation processes have been identified as (i) for the metastable state, collisional deexcitation by thallium halide molecules at high halide densities (≥1015 cm−3) and by free halogens and trace impurities at lower halide densities and (ii) for the ground state, diffusion in the ambient (argon/thallium halide) gas at high halide densities and volume reassociation under certain conditions at low halide densities. Cross sections and diffusion coefficients are evaluated.