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Physical Review

Atomic Absorption Cross Section of Sodium Vapor Between 2400 and 1000 Å

R. D. Hudson

Published Aug 31, 1964• 44 citations
Publisher

Abstract

The continuous atomic absorption cross section of sodium vapor has been measured using photoelectric techniques from the $3s^{2}S\ensuremath{\rightarrow}\mathrm{np}^{2}P^{0}$ series limit at 2412.6 \AA{}, down to 1000 \AA{}. The bandwidth of the monochromator was 1 \AA{}, and values of the cross section were obtained at about 2-\AA{} intervals. The best value for the atomic absorption cross section at the series limit was 0.130\ifmmode\pm\else\textpm\fi{}0.018 Mb. A zero minimum was observed at 1950 \AA{}, in agreement with theoretical predictions but conflicting with previous experimental results. The reasons for this conflict are discussed, and a description is given of the experimental procedures adopted.

DOI
10.1103/physrev.135.a1212

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The continuous atomic absorption cross section of sodium vapor has been measured using photoelectric techniques from the 3s2S\ensuremath→np2P03s^{2}S\ensuremath{\rightarrow}\mathrm{np}^{2}P^{0}3s2S\ensuremath→np2P0 series limit at 2412.6 \AA{}, down to 1000 \AA{}. The bandwidth of the monochromator was 1 \AA{}, and values of the cross section were obtained at about 2-\AA{} intervals. The best value for the atomic absorption cross section at the series limit was 0.130\ifmmode\pm\else\textpm\fi{}0.018 Mb. A zero minimum was observed at 1950 \AA{}, in agreement with theoretical predictions but conflicting with previous experimental results. The reasons for this conflict are discussed, and a description is given of the experimental procedures adopted.
Abstract The first section of this paper is an account of some experiments on the absorption of light in sodium vapour from the series limit at 2412 Å to about 1600 Å (an energy difference of 2·6 eV). The absorption cross-section at the limit is 11·6 ± 1·2 x 10-20 cm2. The cross-section decreases giving a minimum of 1·3 ± 0·6 x 10-20 cm2 at 1900 Å and then increases to 1600 Å. A theoretical calculation by Seaton based on the dipole-length formula gives good agreement with the experiments at the series limit and also correctly predicts the wave-length for the minimum, but it predicts a significantly lower absorption at the minimum. The experiments described in the first section of the paper conclude a series on the absorption of light in the alkali metals. The second section consists of a general discussion of the results of these experiments and of their relation to theoretical calculations. There is good agreement between theory and experiment except in regard to the magnitude of the absorption at the minimum.
The total cross sections for inelastic collisions between sodium and inert gas atoms, leading to 3 2P1/2 ↔ 3 2P3/2 excitation transfer in sodium, have been determined in a series of sensitized fluorescence experiments with sodium – inert gas mixtures. The sodium vapor was maintained at a pressure of 5 × 10−7 mm Hg, at which there is no trapping of the resonance radiation, and the inert gas pressures ranged from 0 to 1 mm Hg. The cross sections Q1(3 2P1/2 → 3 2P3/2) and Q2(3 2P1/2 ← 3 2P3/2) are as follows: Na–He, 86.0 and 44.8 Å2; Na–Ne, 67.0 and 35.4 Å2; Na–Ar, 110 and 55.9 Å2; Na–Kr, 85.0 and 43.6 Å2; Na–Xe, 89.8 and 45.6 Å2. The ratios Q1/Q2 are in agreement with the value predicted from the principle of detailed balancing and the cross sections also agree, as to order of magnitude, with some theoretically predicted values.
An electron and photon atomic-recoil technique has been used to measure absolute total cross sections for electrons scattered by 32{3}^{2}32P3/2{P}_{3/2}P3/2​ sodium atoms in the 6--25-eV energy range, with the use of a new, high-resolution crossed-beam apparatus. A single-mode tunable ring dye laser is used to selectively excite the F=3 hyperfine level. Excited-state populations are determined by using the atomic recoil in resonant photon absorption. At 6 eV there is very good agreement with a previous measurement [B. Jaduszliwer, R. Dang, P. Weiss, and B. Bederson, Phys. Rev. A 21, 808 (1980)].
The intensity ratio D2/D1 for the sodium doublet has been measured for radiation from excited sodium atoms which result from the optical dissociation of sodium iodide vapor by ultraviolet light in the 2082→2500 A region. With shorter wavelength ultraviolet light as exciting source, the D2/D1 ratio is 0.98 and increases to above 1.5 with longer exciting wavelengths. Addition of foreign gases cause the observed D2/D1 ratio to increase to 1.89 for large foreign gas pressure. Cross sections for the transfer of excited sodium atoms from the 32P32 to the 32P½ state and vice versa due to collisions with foreign molecules have been measured as they depend on the relative velocity between excited sodium atom and foreign molecule. The Doppler broadening of the separate D lines emitted in the atomic fluorescence of sodium iodide has been estimated from absorption measurements. Both lines show equal broadening within the experimental error of the observations. Measurements were made with a photomultiplier tube. The sodium doublet was resolved with a reflection grating monochromator.
The resonance broadening of the sodium D-lines in absorption was determined by measuring the contour of the line wings directly. The vapor pressures of sodium ranged from 10-3 to 75 mm Hg, with negligible amount of foreign gases. Over nearly the entire range, the half-intensity width varied linearly with the density of the absorbing atoms; i.e. Δν1/2/N = 0.78 x 10-7 sec-1cm3 --the constant being about twice that predicted by Houston, but much less than the experimental result by Hughes and LLoyd. Above 5 mm pressure, the half-intensity width appeared to increase slightly faster than N. Somewhat in contradiction to theory, the relative width, Δν1/2,s/Δν1/2,1' was 1.16. The natural width measured was, within experimental error, consistent with previous values. The inverse square contour for the absorption coefficient was satisfactory up to 5 mm Hg; beyond this pressure an inverse cube contour fitted better. No definite evidence of van der Waal force was observed at high pressures; likewise, no appreciable shifts and asymmetries. MgO windows were used and the temperature determination was made reliable.