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Canadian Journal of Physics

SENSITIZED FLUORESCENCE IN VAPORS OF ALKALI METALS: IV. ENERGY TRANSFER IN RUBIDIUM–RUBIDIUM COLLISIONS

A. G. A. Rae, L. Krause

Published Sep 1, 1965• 11 citations
Publisher

Abstract

Sensitized fluorescence in rubidium vapor has been investigated in order to determine total cross sections for collisions of the second kind between rubidium atoms, leading to the transfer of excitation between the 5 2P1/2 and 5 2P3/2 resonance levels. The experiments were carried out at vapor pressures below 10−5 mm Hg, where there is virtually no imprisonment of resonance radiation. The exceedingly low fluorescent intensities were registered in an automatically programmed sequence of measurements, using photon counting techniques. The cross sections Q1(5 2P1/2 → 52P3/2) and Q2(5 2P1/2 ← 5 2P3/2) equal 53 Å2 and 68 Å2 respectively at 87 °C and 60 Å2 and 72 Å2 respectively at 107 °C. At both temperatures the ratios Q1/Q2 are in agreement with the values predicted by the principle of detailed balancing.

DOI
10.1139/p65-149

Related papers

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

Bruce Pitre, A. G. A. Rae, L. Krause

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 METALS: VII. ENERGY TRANSFER IN RUBIDIUM–CESIUM COLLISIONS

M. Czajkowski, D. A. McGillis, L. Krause

Sensitized fluorescence in cesium vapor induced by collisions with excited rubidium atoms was investigated in order to determine the total cross sections for inelastic collisions between excited rubidium atoms and cesium atoms in their ground states. The partial pressure of the rubidium vapor in the Rb–Cs mixture was kept below 2 × 10−5 mm Hg in order to eliminate effects due to the trapping of the Rb resonance radiation. The collision cross sections for the various excitation transfer processes are as follows: Q12′(Rb 5 2P1/2 → Cs 6 2P3/2) = 1.5 Å2; Q11′(Rb 5 2P1/2 → Cs 6 2P1/2) = 0.5 Å2; Q22′(Rb 5 2P3/2 → Cs 6 2P3/2) = 0.9 Å2; Q21′(Rb 5 2P3/2 → Cs 6 2P1/2) = 0.3 Å2. The fact that the cross sections are considerably smaller than those for collisions between similar atoms indicates that the Rb–Cs interactions probably involve van der Waals' forces with a much shorter range than exchange forces, which play a dominant role in Rb–Rb or Cs–Cs collisions.

Canadian Journal of Physics•Apr 1, 1966•18 citations

SENSITIZED FLUORESCENCE IN VAPORS OF ALKALI METALS: III. ENERGY TRANSFER IN CESIUM–CESIUM COLLISIONS

M. Czajkowski, L. Krause

Collisions of the second kind leading to the transfer of excitation between 6 2P1/2 and 6 2P3/2 states in cesium have been investigated by studying sensitized fluorescence in cesium vapor at pressures in the range 2 × 10−6 to 7 × 10−5 mm Hg, which were not accessible previously to such experiments and at which trapping of resonance radiation is virtually absent. The use of an improved fluorescence tube and of high-resolution interference filters in conjunction with a liquid-air-cooled photomultipler tube permitted accurate measurements of extremely low fluorescent light intensities. The total cross sections for the processes 6 2P1/2 → 6 2P3/2 and 6 2P1/2 ← 6 2P3/2 equal 0.64 × 10−15 cm2 and 3.1 × 10−15 cm2 respectively and are in a ratio of 0.20, which agrees well with the value predicted by the principle of detailed balancing.

Canadian Journal of Physics•Jul 1, 1965•30 citations

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

John M. Pitre, L. Krause

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.

Canadian Journal of Physics•Aug 1, 1967•69 citations

SENSITIZED FLUORESCENCE IN VAPORS OF ALKALI METALS: II. ENERGY TRANSFER IN POTASSIUM–ARGON COLLISIONS

G. D. Chapman, L. Krause

Sensitized fluorescence in potassium, induced by argon at pressures between 0.01 mm Hg and 350 mm Hg, was investigated to determine the cross sections for collisions of the second kind between potassium atoms in the 4 2P states and argon atoms in their ground states. The experiment was carried out at a potassium vapor pressure of 2 × 10−6 mm Hg at which there is no trapping of resonance radiation. The collision cross sections at very low argon pressures, at which the collision frequencies do not exceed one per average lifetime of the excited states, are Q1 = 10 × 10−15 cm2 for the 4 2P1/2 → 4 2P3/2 transition and Q2 = 7.2 × 10−15 cm2 for the 4 2P1/2 ← 4 2P3/2 transition. At higher pressures, where the collisions are much more frequent, Q1 = 1.8 × 10−15 cm2, Q2 = 1.1 × 10−15 cm2, and Q1/Q2 = 1.6, in exact agreement with the principle of detailed balancing. The variation of the collision cross sections with argon pressure is ascribed to different transfer mechanisms predominating in the various pressure regions.

Canadian Journal of Physics•Apr 1, 1965•12 citations

Sensitized fluorescence in vapors of alkali metals. XII. 42P1/2–42P3/2 mixing in potassium, induced in collisions with ground-state rubidium atoms

E. S. Hrycyshyn, L. Krause

The total cross sections for collisions between excited potassium and unexcited rubidium atoms, leading to the transfer of excitation between the 42P states in potassium, have been determined in a sensitized fluorescence experiment. The experiments were carried out at partial pressures of potassium vapor lower than 10−5 mm Hg, at which the imprisonment of resonance radiation may be disregarded. The cross sections Q12″ (42P1/2 → 42P3/2) and Q21″ (42P1/2 ← 42P3/2) equal 260 Å2 and 175 Å2, respectively, and are in the ratio predicted by the principle of detailed balancing.

Canadian Journal of Physics•Jan 15, 1969•9 citations
Sensitized fluorescence in rubidium vapor has been investigated in order to determine total cross sections for collisions of the second kind between rubidium atoms, leading to the transfer of excitation between the 5 2P1/2 and 5 2P3/2 resonance levels. The experiments were carried out at vapor pressures below 10−5 mm Hg, where there is virtually no imprisonment of resonance radiation. The exceedingly low fluorescent intensities were registered in an automatically programmed sequence of measurements, using photon counting techniques. The cross sections Q1(5 2P1/2 → 52P3/2) and Q2(5 2P1/2 ← 5 2P3/2) equal 53 Å2 and 68 Å2 respectively at 87 °C and 60 Å2 and 72 Å2 respectively at 107 °C. At both temperatures the ratios Q1/Q2 are in agreement with the values predicted by the principle of detailed balancing.
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.
Sensitized fluorescence in cesium vapor induced by collisions with excited rubidium atoms was investigated in order to determine the total cross sections for inelastic collisions between excited rubidium atoms and cesium atoms in their ground states. The partial pressure of the rubidium vapor in the Rb–Cs mixture was kept below 2 × 10−5 mm Hg in order to eliminate effects due to the trapping of the Rb resonance radiation. The collision cross sections for the various excitation transfer processes are as follows: Q12′(Rb 5 2P1/2 → Cs 6 2P3/2) = 1.5 Å2; Q11′(Rb 5 2P1/2 → Cs 6 2P1/2) = 0.5 Å2; Q22′(Rb 5 2P3/2 → Cs 6 2P3/2) = 0.9 Å2; Q21′(Rb 5 2P3/2 → Cs 6 2P1/2) = 0.3 Å2. The fact that the cross sections are considerably smaller than those for collisions between similar atoms indicates that the Rb–Cs interactions probably involve van der Waals' forces with a much shorter range than exchange forces, which play a dominant role in Rb–Rb or Cs–Cs collisions.
Collisions of the second kind leading to the transfer of excitation between 6 2P1/2 and 6 2P3/2 states in cesium have been investigated by studying sensitized fluorescence in cesium vapor at pressures in the range 2 × 10−6 to 7 × 10−5 mm Hg, which were not accessible previously to such experiments and at which trapping of resonance radiation is virtually absent. The use of an improved fluorescence tube and of high-resolution interference filters in conjunction with a liquid-air-cooled photomultipler tube permitted accurate measurements of extremely low fluorescent light intensities. The total cross sections for the processes 6 2P1/2 → 6 2P3/2 and 6 2P1/2 ← 6 2P3/2 equal 0.64 × 10−15 cm2 and 3.1 × 10−15 cm2 respectively and are in a ratio of 0.20, which agrees well with the value predicted by the principle of detailed balancing.
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.
Sensitized fluorescence in potassium, induced by argon at pressures between 0.01 mm Hg and 350 mm Hg, was investigated to determine the cross sections for collisions of the second kind between potassium atoms in the 4 2P states and argon atoms in their ground states. The experiment was carried out at a potassium vapor pressure of 2 × 10−6 mm Hg at which there is no trapping of resonance radiation. The collision cross sections at very low argon pressures, at which the collision frequencies do not exceed one per average lifetime of the excited states, are Q1 = 10 × 10−15 cm2 for the 4 2P1/2 → 4 2P3/2 transition and Q2 = 7.2 × 10−15 cm2 for the 4 2P1/2 ← 4 2P3/2 transition. At higher pressures, where the collisions are much more frequent, Q1 = 1.8 × 10−15 cm2, Q2 = 1.1 × 10−15 cm2, and Q1/Q2 = 1.6, in exact agreement with the principle of detailed balancing. The variation of the collision cross sections with argon pressure is ascribed to different transfer mechanisms predominating in the various pressure regions.
The total cross sections for collisions between excited potassium and unexcited rubidium atoms, leading to the transfer of excitation between the 42P states in potassium, have been determined in a sensitized fluorescence experiment. The experiments were carried out at partial pressures of potassium vapor lower than 10−5 mm Hg, at which the imprisonment of resonance radiation may be disregarded. The cross sections Q12″ (42P1/2 → 42P3/2) and Q21″ (42P1/2 ← 42P3/2) equal 260 Å2 and 175 Å2, respectively, and are in the ratio predicted by the principle of detailed balancing.