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The Journal of Chemical Physics

Long-range interactions of the thallium 7 2S1/2 state and broadening and shift of the thallium violet and green lines by rare gases

Chao Wu, William C. Stwalley, Timothy R. Proctor

Published Nov 1, 1978• 6 citations
Publisher

Abstract

The long-range interaction coefficients (C6, C8, C10) of the Tl(7 S1/2) atom with rare gases are calculated. The pressure-induced broadening and shift of the thallium resonance lines in the presence of rare gases are then calculated using these long-range coefficients and impact theory. We find that higher order van der Waals forces are not negligible compared to the leading −C6/R6 dispersion force in terms of their contributions to the broadening and shift.

DOI
10.1063/1.437107

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Collisional broadening and shift of Doppler-free two-photon thallium lines perturbed by rare-gas atoms

Andrzej Bielski, R. Ciuryło, J. Domysławska +1 more

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The European Physical Journal D•Jan 1, 1999•2 citations
The long-range interaction coefficients (C6, C8, C10) of the Tl(7 S1/2) atom with rare gases are calculated. The pressure-induced broadening and shift of the thallium resonance lines in the presence of rare gases are then calculated using these long-range coefficients and impact theory. We find that higher order van der Waals forces are not negligible compared to the leading −C6/R6 dispersion force in terms of their contributions to the broadening and shift.
The broadening and shift of two-photon $S\ensuremath{-}S$ transitions (e.g., in alkali-metal atoms perturbed by rare gases) are shown to be readily calculable. These calculations employ (a) newly available expressions for alkalimetal-rare-gas long-range potential coefficients C6{C}_{6}C6​, C8{C}_{8}C8​, and C10{C}_{10}C10​; and (b) the (herein discussed) appropriate form of impact theory (particularly simple since only a single potential curve is involved and inelastic processes are not usually important). It is demonstrated in particular that the influence of C8{C}_{8}C8​ and C10{C}_{10}C10​ terms on the broadening and shift is significant though not dominant. Comparison with recent experimental data on the Na-rare-gas pairs shows reasonable agreement for the heavy rare gases.
Broadening and shift rates by rare gases have been measured for the Tl transitions 6P1/2{\mathit{P}}_{1/2}P1/2​-nP1/2,3/2{\mathit{nP}}_{1/2,3/2}nP1/2,3/2​ (n=9-14) applying Doppler-free two-photon spectroscopy. The rates show a clearly significant dependence on the total angular momentum of the upper nP states and also a distinct behavior over the most interesting range of intermediate effective principle quantum numbers. Calculations using a van der Waals potential and a combination of polarization and Fermi pseudopotential describe these dependences well. \textcopyright{} 1996 The American Physical Society.
Reports the results of interferometric investigation of collisional broadening and shift of the resonance line of thallium ( lambda =377.68 nm) by krypton and xenon. The measurements were performed at low density of the perturbing gases (3-53*10 16 cm -3 ) and both Doppler and collisional broadening of the line were determined. The results are compared with those calculated on the basis of the van der Waals, Lennard-Jones and Czuchaj-Sienkiewicz potentials. The measured values of the broadening and shift by krypton and xenon are lower than those computed for the van der Waals and Lennard-Jones potentials. Calculations based on realistic potentials reported by Czuchaj and Sienkiewicz give values of the broadening coefficient in good agreement with the experimental data.
We present semiempirical calculations of long-range van der Waals interactions for two interacting metastable rare-gas atoms Ne through Xe. Dispersion coefficients C6{C}_{6}C6​ are obtained for homonuclear molecular potentials asymptotically connecting to the ns(3/2)2+ns(3/2)2{\mathrm{ns}(3/2)}_{2}{+ns(3/2)}_{2}ns(3/2)2​+ns(3/2)2​ atomic states. The estimated uncertainty of the calculated C6{C}_{6}C6​ dispersion coefficients is 4%.