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Journal of the Optical Society of America

Absorption Bands of Rubidium due to the Presence of Foreign Gases*

Shang-Yi Ch’en, Robert B. Bennett, Oleg D. Jefimenko

Published Mar 1, 1956• 22 citations
Publisher

Abstract

In the presence of heavy foreign gases, such as Kr and Xe, diffused absorption bands were observed at both the short wavelength and the long wavelength side of the first four absorption doublets of the Rb principal series. The red bands were observable when the Rb vapor pressure in the absorption tube was relatively low (10−3 to 10−2 mm Hg). The violet bands were not intense enough until the Rb vapor pressure was increased to 0.1–1 mm Hg. With other lighter gases (H2, He, Ne, A, N2) only violet bands were observed. The positions and the absorption contours of the bands in relation to the member of the absorption series and to the nature of the foreign gases are discussed.

DOI
10.1364/josa.46.000182

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Pressure Effects of Homogeneous Rubidium Vapor on Its Resonance Lines

Shang-Yi Ch'en

The broadening of the resonance lines of rubidium in absorption under pressures up to 150 mm of its own homogeneous vapor was studied by means of a 21-foot grating. Under pressures below 1 mm the broadening of the lines was very symmetrical and the line contours could be described by the dispersion formula, but when the pressure was high the lines exhibited asymmetrical broadening of van der Waals type. The $^{2}P_{\frac{1}{2}}$ component showed red, while the $^{2}P_{\frac{3}{2}}$ component showed violet asymmetry. Both lines showed the proportionality of the width with $N$, the concentration of Rb atoms. The experimental width at half-maximum is greater than that predicted by Houston's theory by a factor of 1.5 and the width of the transition from $^{3}P_{\frac{3}{2}}$ is greater than that from $^{3}P_{\frac{1}{2}}$ by a factor of 1.6. A narrow diffuse band was observed near the shorter wave-length side of the $^{2}P_{\frac{1}{2}}$ component and a similar one near the longer wave-length side of the $^{2}P_{\frac{3}{2}}$ component.

Physical Review•Nov 15, 1940•40 citations

Pressure Effects of Rare Gases on the Second Doublet of Rubidium Principal Series

Ny Tsi-Zé, Shang-Yi Ch'en

The displacement, asymmetry, and broadening of the second doublet of the rubidium principal series perturbed by pure helium, neon and argon up to 13 atmospheres are observed. The displacement as well as the broadening of the doublet components are not the same. The $^{2}P_{\frac{1}{2}}$ component shifts and broadens more conspicuously than the $^{2}P_{1\frac{1}{2}}$ component (an exception being the broadening by argon). The departure from linear relationship between the shift and the density of the perturbing gas is quite manifest. Both for helium and for neon the line contour shows a distinct asymmetry towards the violet, while for argon the line contour shows a very strong red asymmetry. For helium and neon the violet asymmetries of the $^{2}P_{\frac{1}{2}}$ component are stronger than that of the $^{2}P_{1\frac{1}{2}}$ component; the reverse is true for argon. The relationship between the half-width and the relative density is linear for foreign gas concentrations of relative densities up to 8 so far applied.

Physical Review•Dec 1, 1937•16 citations

SENSITIZED FLUORESCENCE IN VAPORS OF ALKALI METALS: VI. ENERGY TRANSFER IN COLLISIONS BETWEEN RUBIDIUM AND INERT GAS ATOMS

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The total cross sections for inelastic collisions between rubidium and inert gas atoms, leading to a transfer of excitation between the 5 2P1/2 and 5 2P3/2 levels in rubidium, have been determined in a study of sensitized fluorescence in rubidium – inert gas mixtures. The experiments were performed at a rubidium vapor pressure of 1.5 × 10−6 mm Hg, at which there is no imprisonment of resonance radiation, and over a range of inert gas pressures extending from 1 to 350 mm Hg. The cross sections Q1(5 2P1/2 → 5 2P3/2) and Q2(5 2P1/2 ← 5 2P3/2) are as follows: Rb–He: 7.6 × 10−18 and 10.3 × 10−18 cm2; Rb–Ne: 1.7 × 10−19 and 2.3 × 10−19 cm2; Rb–A: 1.0 × 10−19 and 1.6 × 10−19 cm2; Rb–Kr: 6.4 × 10−20 and 1.5 × 10−19 cm2; Rb–Xe: 7.9 × 10−20 and 2.1 × 10−19 cm2. The cross sections are subject to two apparent anomalies: they do not vary monotonically with the polarizabilities of the inert gases and not all of their ratios Q1/Q2 have values predicted by the principle of detailed balancing. These properties of the cross sections, as well as a partial disagreement with Franck's rule, are interpreted qualitatively in terms of a "free particle" interaction between the inert gas atoms and the 5 2P orbital electron in rubidium. A competing process involving three-body collisions and the possible formation of Rb – inert gas van der Waals' molecules is also suggested.

Canadian Journal of Physics•Apr 1, 1966•38 citations

Sensitized Fluorescence in Vapors of Alkali Atoms. XIII. 62P1/2−62P3/2 Excitation Transfer in Rubidium, Induced in Collisions with Noble Gas Atoms

I. N. Siara, E. S. Hrycyshyn, L. Krause

The cross sections for excitation transfer between the 62P fine-structure substates in rubidium, induced in collisions with noble gas atoms, have been determined in a series of sensitized fluorescence experiments. Mixtures of rubidium vapor and noble gases at pressures varying in the range 0–5 Torr were irradiated with each component of the second 2P rubidium doublet in turn and the following cross sections for 2P mixing were obtained from measurements of sensitised-to-resonance fluorescent intensity ratios. Rb–He: Q12(2P1/2 → 2P3/2) = 29.3 Å2; Q21(2P1/2 ← 2P3/2) = 19.0 Å2. Rb–Ne: Q12 = 10.3 Å2; Q21 = 6.4 Å2. Rb–Ar: Q12 = 24.0 Å2; Q21 = 14.9 Å2. Rb–Kr: Q12 = 23.2 Å2; Q21 = 14.6 Å2. Rb–Xe: Q12 = 43.9 Å2; Q21 = 27.7 Å2 In their dependence on the magnitude of the fine-structure splitting, the values are consistent with previously determined cross sections for mixing in the first and third 2P doublets of alkali atoms.

Canadian Journal of Physics•Aug 15, 1972•19 citations

Broadening and Shift of the Second Doublet of the Rubidium Absorption Series Under Different Pressures of Argon and Helium

Shang-Yi Ch'en, D. Kohler

The shift and broadening of the second doublet of the principal series of rubidium produced by argon and by helium were studied for pressures up to 123.5 atmospheres (rd 52) and up to 97.5 atmospheres (rd 44), respectively. The red shift produced by argon gives a linear relationship with its relative density, rd. The slopes for both components of the doublet are 2.95 ${\mathrm{cm}}^{\ensuremath{-}1}$/rd. The violet shift produced by helium in the high pressure range is greater than linear with the rd. The $^{2}P_{\frac{1}{2}}$ component is shifted more than the $^{2}P_{\frac{3}{2}}$ component.Argon shows a nicely linear broadening for both components over the entire range of rd. For the $^{2}P_{\frac{3}{2}}$ component the broadening is 2.28 ${\mathrm{cm}}^{\ensuremath{-}1}$/rd and for the $^{2}P_{\frac{1}{2}}$ component it is 2.11 ${\mathrm{cm}}^{\ensuremath{-}1}$/rd. Helium appears to give a definite quadratic broadening, particularly for the $^{2}P_{\frac{3}{2}}$ component.

Physical Review•Jun 15, 1953•8 citations

Spectroscopic studies of alkali atom-rare gas systems

Steven J. Davis, Kristin L. Galbally-Kinney, William J. Kessler +1 more

We describe a series of measurements of absorption and laser induced fluorescence on cells that contained cesium and rubidium and a rare gas: He, Ar, Kr, or Xe. These studies showed strong blue wing absorption to the short wavelength side of the alkali atom D2 lines due to collisionally formed Cs- or Rb-rare gas excimers. We also have observed an efficient two photon excitation of higher lying states in Cs and Rb that produces both intense blue emission and IR atomic emission in the 1.3 to 3.8 μm spectral region.

Proceedings of SPIE, the International Society for Optical Engineering/Proceedings of SPIE•Feb 11, 2010•3 citations
In the presence of heavy foreign gases, such as Kr and Xe, diffused absorption bands were observed at both the short wavelength and the long wavelength side of the first four absorption doublets of the Rb principal series. The red bands were observable when the Rb vapor pressure in the absorption tube was relatively low (10−3 to 10−2 mm Hg). The violet bands were not intense enough until the Rb vapor pressure was increased to 0.1–1 mm Hg. With other lighter gases (H2, He, Ne, A, N2) only violet bands were observed. The positions and the absorption contours of the bands in relation to the member of the absorption series and to the nature of the foreign gases are discussed.
The broadening of the resonance lines of rubidium in absorption under pressures up to 150 mm of its own homogeneous vapor was studied by means of a 21-foot grating. Under pressures below 1 mm the broadening of the lines was very symmetrical and the line contours could be described by the dispersion formula, but when the pressure was high the lines exhibited asymmetrical broadening of van der Waals type. The 2P12^{2}P_{\frac{1}{2}}2P21​​ component showed red, while the 2P32^{2}P_{\frac{3}{2}}2P23​​ component showed violet asymmetry. Both lines showed the proportionality of the width with NNN, the concentration of Rb atoms. The experimental width at half-maximum is greater than that predicted by Houston's theory by a factor of 1.5 and the width of the transition from 3P32^{3}P_{\frac{3}{2}}3P23​​ is greater than that from 3P12^{3}P_{\frac{1}{2}}3P21​​ by a factor of 1.6. A narrow diffuse band was observed near the shorter wave-length side of the 2P12^{2}P_{\frac{1}{2}}2P21​​ component and a similar one near the longer wave-length side of the 2P32^{2}P_{\frac{3}{2}}2P23​​ component.
The displacement, asymmetry, and broadening of the second doublet of the rubidium principal series perturbed by pure helium, neon and argon up to 13 atmospheres are observed. The displacement as well as the broadening of the doublet components are not the same. The 2P12^{2}P_{\frac{1}{2}}2P21​​ component shifts and broadens more conspicuously than the 2P112^{2}P_{1\frac{1}{2}}2P121​​ component (an exception being the broadening by argon). The departure from linear relationship between the shift and the density of the perturbing gas is quite manifest. Both for helium and for neon the line contour shows a distinct asymmetry towards the violet, while for argon the line contour shows a very strong red asymmetry. For helium and neon the violet asymmetries of the 2P12^{2}P_{\frac{1}{2}}2P21​​ component are stronger than that of the 2P112^{2}P_{1\frac{1}{2}}2P121​​ component; the reverse is true for argon. The relationship between the half-width and the relative density is linear for foreign gas concentrations of relative densities up to 8 so far applied.
The total cross sections for inelastic collisions between rubidium and inert gas atoms, leading to a transfer of excitation between the 5 2P1/2 and 5 2P3/2 levels in rubidium, have been determined in a study of sensitized fluorescence in rubidium – inert gas mixtures. The experiments were performed at a rubidium vapor pressure of 1.5 × 10−6 mm Hg, at which there is no imprisonment of resonance radiation, and over a range of inert gas pressures extending from 1 to 350 mm Hg. The cross sections Q1(5 2P1/2 → 5 2P3/2) and Q2(5 2P1/2 ← 5 2P3/2) are as follows: Rb–He: 7.6 × 10−18 and 10.3 × 10−18 cm2; Rb–Ne: 1.7 × 10−19 and 2.3 × 10−19 cm2; Rb–A: 1.0 × 10−19 and 1.6 × 10−19 cm2; Rb–Kr: 6.4 × 10−20 and 1.5 × 10−19 cm2; Rb–Xe: 7.9 × 10−20 and 2.1 × 10−19 cm2. The cross sections are subject to two apparent anomalies: they do not vary monotonically with the polarizabilities of the inert gases and not all of their ratios Q1/Q2 have values predicted by the principle of detailed balancing. These properties of the cross sections, as well as a partial disagreement with Franck's rule, are interpreted qualitatively in terms of a "free particle" interaction between the inert gas atoms and the 5 2P orbital electron in rubidium. A competing process involving three-body collisions and the possible formation of Rb – inert gas van der Waals' molecules is also suggested.
The cross sections for excitation transfer between the 62P fine-structure substates in rubidium, induced in collisions with noble gas atoms, have been determined in a series of sensitized fluorescence experiments. Mixtures of rubidium vapor and noble gases at pressures varying in the range 0–5 Torr were irradiated with each component of the second 2P rubidium doublet in turn and the following cross sections for 2P mixing were obtained from measurements of sensitised-to-resonance fluorescent intensity ratios. Rb–He: Q12(2P1/2 → 2P3/2) = 29.3 Å2; Q21(2P1/2 ← 2P3/2) = 19.0 Å2. Rb–Ne: Q12 = 10.3 Å2; Q21 = 6.4 Å2. Rb–Ar: Q12 = 24.0 Å2; Q21 = 14.9 Å2. Rb–Kr: Q12 = 23.2 Å2; Q21 = 14.6 Å2. Rb–Xe: Q12 = 43.9 Å2; Q21 = 27.7 Å2 In their dependence on the magnitude of the fine-structure splitting, the values are consistent with previously determined cross sections for mixing in the first and third 2P doublets of alkali atoms.
The shift and broadening of the second doublet of the principal series of rubidium produced by argon and by helium were studied for pressures up to 123.5 atmospheres (rd 52) and up to 97.5 atmospheres (rd 44), respectively. The red shift produced by argon gives a linear relationship with its relative density, rd. The slopes for both components of the doublet are 2.95 ${\mathrm{cm}}^{\ensuremath{-}1}$/rd. The violet shift produced by helium in the high pressure range is greater than linear with the rd. The 2P12^{2}P_{\frac{1}{2}}2P21​​ component is shifted more than the 2P32^{2}P_{\frac{3}{2}}2P23​​ component.Argon shows a nicely linear broadening for both components over the entire range of rd. For the 2P32^{2}P_{\frac{3}{2}}2P23​​ component the broadening is 2.28 ${\mathrm{cm}}^{\ensuremath{-}1}$/rd and for the 2P12^{2}P_{\frac{1}{2}}2P21​​ component it is 2.11 ${\mathrm{cm}}^{\ensuremath{-}1}$/rd. Helium appears to give a definite quadratic broadening, particularly for the 2P32^{2}P_{\frac{3}{2}}2P23​​ component.
We describe a series of measurements of absorption and laser induced fluorescence on cells that contained cesium and rubidium and a rare gas: He, Ar, Kr, or Xe. These studies showed strong blue wing absorption to the short wavelength side of the alkali atom D2 lines due to collisionally formed Cs- or Rb-rare gas excimers. We also have observed an efficient two photon excitation of higher lying states in Cs and Rb that produces both intense blue emission and IR atomic emission in the 1.3 to 3.8 μm spectral region.