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

1965 ◽  
Vol 43 (4) ◽  
pp. 563-575 ◽  
Author(s):  
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.

1969 ◽  
Vol 47 (2) ◽  
pp. 223-226 ◽  
Author(s):  
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.


1966 ◽  
Vol 44 (4) ◽  
pp. 753-768 ◽  
Author(s):  
G. D. Chapman ◽  
L. Krause

Sensitized fluorescence in potassium vapor and its mixtures with inert gases was investigated in order to determine cross sections for the inelastic collisions leading to excitation transfer between the 4 2P1/2 and 4 2P3/2 states in potassium. The study was carried out at potassium vapor pressures of about 10−6 mm Hg, which were not formerly accessible to such experiments, and in the absence of radiation trapping. The cross sections Q1(4 2P1/2 → 42P3/2) and Q2(4 2P1/2 → 4 2P3/2) are as follows: for K–K collisions: 370 and 250 Å2; for K–He: 60 and 41 Å2; for K–Ne: 14 and 9.5 Å2; for K–A: 37 and 22 Å2; for K–Kr: 61 and 41 Å2; for K–Xe: 104 and 72 Å2. These values supersede those published previously (Chapman, Krause, and Brockman 1964; Chapman and Krause 1965). The cross sections for collisions between potassium and inert gas atoms do not increase monotonically with the polarizabilities of the inert gases but behave similarly to the electron – inert gas elastic scattering cross sections. This behavior is interpreted on the basis of a semiclassical model for the interaction, which involves overlap forces.


1964 ◽  
Vol 42 (3) ◽  
pp. 535-547 ◽  
Author(s):  
G. D. Chapman ◽  
L. Krause ◽  
I. H. Brockman

Sensitized fluorescence in potassium vapor at pressures between 10−5 mm Hg and 10−1 mm Hg was investigated to determine the cross sections for collisions of the second kind between unexcited and excited potassium atoms. An idealized fluorescence tube was used in the experiment and the fluorescent light was analyzed with a photoelectric recording spectrometer. The collision cross sections at low vapor pressures, where imprisonment of radiation is absent, are identical for both the 42P1/2 → 42P3/2 and 42P1/2 ← 42P3/2 transitions and equal 6.6 × 10−12 cm2 at 2 × 10−4 mm Hg. The experimental results are interpreted on the basis of new selection rules for sensitized fluorescence.


1969 ◽  
Vol 47 (2) ◽  
pp. 215-221 ◽  
Author(s):  
E. S. Hrycyshyn ◽  
L. Krause

Sensitized fluorescence in rubidium vapor, induced by collisions with excited potassium atoms, was investigated to determine the total cross sections for inelastic collisions between excited potassium atoms and rubidium atoms in their ground states. The collision cross sections for the various excitation transfer processes are as follows: Q12′ (K42P1/2 → Rb52P3/2) = 40 Å2, Q22′ (K42P3/2 → Rb52P3/2) = 27 Å2, Q11′ (K42P1/2 → Rb52P1/2) = 2.7 Å2, and Q21′ (K42P3/2 → Rb52P1/2) = 1.9 Å2. The partial pressure of potassium vapor in the K–Rb mixture was kept largely below 10−5 mm Hg to eliminate effects due to the trapping of potassium resonance radiation.


1965 ◽  
Vol 43 (9) ◽  
pp. 1574-1588 ◽  
Author(s):  
A. G. A. Rae ◽  
L. Krause

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 52P1/2and 52P3/2resonance 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(52P1/2 → 52P3/2) and Q2(52P1/2 ← 52P3/2) equal 53 Å2and 68 Å2respectively at 87 °C and 60 Å2and 72 Å2respectively at 107 °C. At both temperatures the ratios Q1/Q2are in agreement with the values predicted by the principle of detailed balancing.


1965 ◽  
Vol 43 (7) ◽  
pp. 1259-1268 ◽  
Author(s):  
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.


1968 ◽  
Vol 46 (2) ◽  
pp. 125-128 ◽  
Author(s):  
John Pitre ◽  
L. Krause

The total cross sections for 3 2P1/2–3 2P3/2 mixing collisions between excited and unexcited sodium atoms have been determined in a series of sensitized fluorescence experiments with pure sodium vapor at pressures in the range 0–1.6 × 10−5 mm Hg. The cross section Q2(3 2P1/2 ← 3 2P3/2) was found to be 283 Å2 ± 10%. The cross section Q1(3 2P1/2 → 3 2P3/2) = 532 Å2 was obtained from Q2 through the application of the principle of detailed balancing.


1967 ◽  
Vol 45 (8) ◽  
pp. 2671-2681 ◽  
Author(s):  
John 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.


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