Inelastic collisions between excited alkali atoms and molecules. IV. Sensitized fluorescence and quenching in mixtures of cesium with N2, H2, HD, and D2

1968 ◽  
Vol 46 (9) ◽  
pp. 1051-1057 ◽  
Author(s):  
D. A. McGillis ◽  
L. Krause
Keyword(s):  
Vapor Pressure ◽  
Multiple Scattering ◽  
Cross Sections ◽  
Ground State ◽  
Inelastic Collisions ◽  
Cesium Vapor ◽  
Sensitized Fluorescence ◽  
Alkali Atoms ◽  
Exciting Beam ◽  
Resonance Doublet

6 2P1/2 ↔ 6 2P3/2 mixing and 6 2S1/2 ← 6 2P1/2,3/2 quenching in cesium, induced in collisions with ground state N2, H2, HD, and D2 molecules, have been investigated using techniques of sensitized fluorescence. Mixtures of cesium vapor and the gases, in which the cesium vapor pressure was kept very low to avoid multiple scattering, were irradiated with each component of the cesium resonance doublet in turn. The fluorescence which contained both components of the doublet was observed in a direction perpendicular to that of the exciting beam. Measurements of the relative intensities of the fluorescent components yielded the following cross sections for mixing and quenching. For Cs–N2 collisions: Q12(2P1/2 → 2P3/2) = 4.7 Å2, Q21(2P1/2 ← 2P3/2) = 25 Å2, Q10(2S1/2 ← 2P1/2) = 77 Å2, Q20(2S1/2 ← 2P3/2) = 69 Å2. For Cs–H2 collisions: Q12 = 6.7 Å2, Q21 = 44 Å2, Q10 = 7 Å2, Q20 = 5 Å2. For Cs–HD collisions: Q12 = 4.8 Å2, Q21 = 32 Å2, Q10 = 4 Å2, Q20 = 3 Å2. For Cs–D2 collisions: Q12 = 4.2 Å2, Q21 = 28 Å2, Q10 = 8 Å2, Q20 = 7 Å2. The Cs–N2 and Cs–H2 cross sections supersede the values published previously (McGillis and Krause 1967). The cross sections Q21 appear to exhibit resonances with molecular rotational transitions.

Inelastic collisions between excited alkali atoms and molecules. V. Sensitized fluorescence in mixtures of sodium with N2, H2, HD, and D2

1968 ◽  
Vol 46 (19) ◽  
pp. 2127-2131 ◽  
Author(s):  
M. Stupavsky ◽  
L. Krause
Keyword(s):  
Cross Sections ◽  
Ground State ◽  
Resonance Effect ◽  
Excitation Transfer ◽  
Inelastic Collisions ◽  
Sodium Vapor ◽  
Sensitized Fluorescence ◽  
Atoms And Molecules ◽  
Alkali Atoms ◽  
Exciting Beam

3 2P1/2 ↔ 3 2P3/2 excitation transfer in sodium, induced in inelastic collisions with ground-state N2, H2, HD, and D2 molecules, has been investigated in a series of sensitized fluorescence experiments. Mixtures of sodium vapor at a pressure of 5 × 10−7 Torr, and the gases, were irradiated with each NaD component in turn, and the fluorescence which contained both D components was monitored at right angles to the direction of the exciting beam. Measurements of the relative intensities of the NaD fluorescent components yielded the following collision cross sections for excitation transfer. For Na–N2 collisions: Q12(2P1/2 → P3/2) = 144 Å2, Q21(2P1,2 ← 2P3/2) = 76 Å2 for Na–H2 collisions: Q12 = 80 Å2, Q21 = 42 Å2. For Na–HD collisions: Q12 = 84 Å2, Q21 = 44 Å2. For Na–D2 collisions: Q12 = 98 Å2, Q21 = 52 Å2. The cross sections Q21 exhibit a slight resonance effect between the atomic and molecular rotational transitions.

Inelastic collisions between excited alkali atoms and molecules, III. Sensitized fluorescence and quenching in mixtures of potassium with N2, H2, HD, and D2

1968 ◽  
Vol 46 (1) ◽  
pp. 25-32 ◽  
Author(s):  
D. A. McGillis ◽  
L. Krause
Keyword(s):  
Vapor Pressure ◽  
Cross Sections ◽  
Inelastic Collisions ◽  
Sensitized Fluorescence ◽  
Atoms And Molecules ◽  
Radiation Trapping ◽  
Alkali Atoms ◽  
Resonance Doublet ◽  
Potassium Vapor

4 2P1/2–4 2P3/2 mixing in potassium, induced by collisions with N2, H2, D2, and HD, was studied using techniques of sensitized fluorescence. The potassium vapor-gas systems, in which the potassium vapor pressure was kept very low to avoid radiation trapping, was irradiated with one component of the resonance doublet. The fluorescence which contained both components of the doublet was monitored at right angles to the direction of excitation. The following cross sections for mixing and quenching were obtained from measurements of relative intensities of the fluorescent components. For K–N2 collisions: Q12(2P1/2 → 2P3/2) = 100 Å2, Q21(2P1/2 ← 2P3/2) = 66 Å2, Q10(2S1/2 ← 2P1/2) = 35 Å2, Q20(2S1/2 ←2P3/2) = 39 Å2. For K–H2 collisions: Q12 = 76 Å2, Q21 = 53 Å2, Q10 = 7 Å2, Q20 = 4 Å2. For K–D2: Q12 = 72 Å2, Q21 = 50 Å2, Q10 = 2 Å2, Q20 = 1 Å2. For K–HD: Q12 = 74 Å2, Q21 = 49 Å2, Q20 = 11 Å2, Q20 = 14 Å2. An analysis of these results suggests the presence of resonances with the molecular rotational levels.

Inelastic Collisions between Excited Alkali Atoms and Molecules. VIII. 62P1/2–62P3/2 Mixing and Quenching in Mixtures of Rubidium with H2, HD, D2, N2, CH4, and CD4

1973 ◽  
Vol 51 (3) ◽  
pp. 257-265 ◽  
Author(s):  
I. N. Siara ◽  
L. Krause
Keyword(s):  
Fine Structure ◽  
Cross Sections ◽  
Ground State ◽  
Inelastic Collisions ◽  
Fluorescent Intensity ◽  
Rubidium Vapor ◽  
Sensitized Fluorescence ◽  
Molecular Gases ◽  
Alkali Atoms ◽  
Intensity Ratios

Excitation transfer between the 62P fine-structure substates in rubidium, induced in inelastic collisions with ground-state molecules, has been studied using techniques of sensitized fluorescence. Rubidium vapor in mixtures with various molecular gases was irradiated with each component of the 2P rubidium doublet in turn, and measurements of sensitized-to-resonance fluorescent intensity ratios yielded the following mixing cross sections Q12(2P1/2 → 2P3/2) and Q21(2P1/2 ← 2P3/2), as well as effective quenching cross sections Q1X(2P1/2 → 2XJ″) and Q2X(2P3/2 → 2XJ″). For collisions with H2: Q12(2P1/2 → 2P3/2) = (41 ± 5) Å2; Q21(2P1/2 ← 2P3/2) = (26 ± 3) Å2; Q1X(2P1/2 → 2XJ″) = (36 ± 9) Å2; Q2X(2P3/2 → 2XJ″) = (31 ± 8) Å2. For HD: Q12 = (42 ± 5) Å2; Q21 = (27 ± 4) Å2; Q1X = (47 ± 13) Å2; Q2X = (38 ± 10) Å2. For D2: Q12 = (42 ± 5) Å2; Q21 = (27 ± 4) Å2; Q1X = (28 ± 8) Å2; Q2X = (21 ± 7) Å2. For N2: Q12 = (107 ± 15) Å2; Q21 = (70 ± 10) Å2; Q1X = (128 ± 44) Å2; Q2X = (126 ± 33) Å2. For CH4: Q12 = (38 ± 6) Å2; Q21 = (24 ± 3) Å2; Q1X = (129 ± 41) Å2; Q2X = (114 ± 37) Å2. For CD4: Q12 = (52 ± 7) Å2; Q21 = (34 ± 5) Å2; Q1X = (82 ± 30) Å2; Q2X = (76 ± 22) Å2. An analysis of these results suggests the possibility of resonances with various molecular rotational and vibrational transitions.

Inelastic collisions between excited alkali atoms and molecules. VII. Sensitized fluorescence and quenching in mixtures of rubidium with H2, HD, D2, N2, CH4, CD4, C2H4, and C2.H6

1970 ◽  
Vol 48 (22) ◽  
pp. 2761-2768 ◽  
Author(s):  
E. S. Hrycyshyn ◽  
L. Krause
Keyword(s):  
Cross Sections ◽  
Photon Counting ◽  
Inelastic Collisions ◽  
Exciting Light ◽  
Rubidium Vapor ◽  
Sensitized Fluorescence ◽  
Alkali Atoms ◽  
Order Of Magnitude ◽  
Resonance Doublet ◽  
Intensity Ratios

52P1/2 ↔ 52P3/2 mixing and 52S1/2 ← 52P1/2, 2P3/2 quenching in rubidium, induced in collisions with ground state H2, HD, D2, N2, CH4, CD4, C2H4, and C2H6 molecules, have been investigated using methods of sensitized fluorescence. The rubidium vapor mixed with each of the gases was excited in turn by each component of the rubidium resonance doublet, and the resulting fluorescence, emitted at right angles to the direction of the exciting light, was resolved into the two fine-structure components whose intensity ratios were measured in relation to the gas pressure using photon counting techniques. The measurements yielded the following cross sections for the mixing and quenching collisions.For H2: Q12(2P1/2 → 2P3/2) = 11 Å2, Q21(2P1/2 ← 2P3/2) = 15 Å2, Q10(2S1/2 ← 2P1/2) = 6 Å2, Q20(2S1/2 ← 2P3/2) = 3 Å2.[Formula: see text]The mixing cross sections agree with theoretical values within an order of magnitude.

Sensitized Fluorescence in Sodium Induced in Collisions with Hg(63P1) Atoms

1973 ◽  
Vol 51 (3) ◽  
pp. 334-342 ◽  
Author(s):  
M. Czajkowski ◽  
G. Skardis ◽  
L. Krause
Keyword(s):  
Excitation Energy ◽  
Cross Sections ◽  
Ground State ◽  
Absolute Intensity ◽  
Resonance Radiation ◽  
Inelastic Collisions ◽  
Sensitized Fluorescence ◽  
Subsequent Decay ◽  
Intensity Measurements ◽  
Fluorescent Spectrum

Collisional transfer of excitation from mercury to sodium was investigated using methods of sensitized fluorescence. A mixture of mercury and sodium vapors at low pressure was irradiated with Hg 2537 Å resonance radiation, producing a population of Hg(63P1) atoms whose inelastic collisions with ground-state sodium atoms resulted in a transfer of excitation energy to close-lying S, P, and D states in sodium. The subsequent decay of these states manifested itself in the emission of a sensitized fluorescent spectrum. Absolute intensity measurements on the components of the spectrum yielded 21 cross sections whose magnitudes range from 0.02 to 38.5 Å2 and which exhibit a pronounced resonance with ΔE, the energy defect between Hg (63P1) and the appropriate level in sodium.

Sensitized Fluorescence in Vapors of Alkali Atoms XIV. Temperature Dependence of Cross Sections for 72P1/2–72P3/2 Mixing in Cesium, Induced in Collisions with Noble Gas Atoms

1974 ◽  
Vol 52 (11) ◽  
pp. 945-949 ◽  
Author(s):  
I. N. Siara ◽  
H. S. Kwong ◽  
L. Krause
Keyword(s):  
Temperature Dependence ◽  
Cross Sections ◽  
Noble Gas ◽  
Excitation Transfer ◽  
Sensitized Fluorescence ◽  
Alkali Atoms ◽  
Resonance Doublet ◽  
The Cross ◽  
Adiabatic Case

The cross sections for 72P1/2–72P3/2 excitation transfer in cesium, induced in collisions with noble gas atoms, have been determined in a series of sensitized fluorescence experiments at temperatures ranging from 405 to 630 K. The cross sections which lie in the range 0.06–20 Å2, exhibit a temperature dependence which, however, is less pronounced than in the more adiabatic case of the cesium resonance doublet.

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

1966 ◽  
Vol 44 (4) ◽  
pp. 741-751 ◽  
Author(s):  
M. Czajkowski ◽  
D. A. McGillis ◽  
L. Krause
Keyword(s):  
Cross Sections ◽  
Alkali Metals ◽  
Dominant Role ◽  
Inelastic Collisions ◽  
Cesium Vapor ◽  
Rubidium Vapor ◽  
Total Cross Sections ◽  
Sensitized Fluorescence ◽  
Rubidium Atoms ◽  
Transfer Processes

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.

Inelastic collisions between excited alkali atoms and molecules. VI. Sensitized fluorescence in mixtures of sodium with CH4, CD4, C2H2, C2H4, and C2H6

1969 ◽  
Vol 47 (12) ◽  
pp. 1249-1252 ◽  
Author(s):  
M. Stupavsky ◽  
L. Krause
Keyword(s):  
Cross Sections ◽  
Inelastic Collisions ◽  
Fluorescent Light ◽  
Molecular Gas ◽  
Sodium Vapor ◽  
Total Cross Sections ◽  
Sensitized Fluorescence ◽  
Alkali Atoms ◽  
The Cross ◽  
Good Agreement

The total cross sections for 32P1/2–32P3/2 mixing in sodium, induced in collisions with CH4, CD4, C2H2, C2H4, and C2H6 molecules, have been determined using the method of sensitized fluorescence. The sodium vapor – molecular gas mixtures were irradiated with each NaD component in turn, and the cross sections were obtained from measurements of relative intensities of the two D components present in the fluorescent light. The cross sections are as follows. For CH4: Q12(2P1/2 → 2P3/2) = 148 Å2, Q21(2P1/2 ← 2P3/2) = 77 Å2; for CD4: Q12 = 151 Å2, Q21 = 81 Å2; for C2H2: Q12 = 182 Å2, Q21 = 96 Å2; for C2H4: Q12 = 178 Å2, Q21 = 94 Å2; for C2H6: Q12 = 182 Å2, Q21 = 95 Å2. The cross sections Q21 are in good agreement with the values calculated according to the theory of Callaway and Bauer.

Sensitized fluorescence in thallium induced in collisions with Hg(63P1) atoms

1978 ◽  
Vol 56 (7) ◽  
pp. 891-896 ◽  
Author(s):  
M. K. Wade ◽  
M. Czajkowski ◽  
L. Krause
Keyword(s):  
Cross Sections ◽  
Ground State ◽  
Excitation Transfer ◽  
Resonance Radiation ◽  
Resonance Fluorescence ◽  
Collisional Excitation ◽  
Vapor Mixture ◽  
Sensitized Fluorescence ◽  
Intensity Measurements ◽  
Metallic Vapor

The transfer of excitation from excited mercury atoms to ground-state thallium atoms was investigated using techniques of sensitized fluorescence. A Hg–Tl vapor mixture contained in a quartz cell was irradiated with Hg 2537 Å resonance radiation which caused the mercury atoms to become excited to the 63P1, state. Subsequent collisions between the Hg(63P1) and Tl(62P1/2) atoms resulted in the population of the 82S1/2, 62D, and 72S1/2 thallium states, whose decay gave rise to sensitized fluorescence of wavelengths 3231, 3520, 3776, and 5352 Å. Intensity measurements on the sensitized fluorescence and on the Hg 2537 Å resonance fluorescence, observed at right angles to the direction of excitation, yielded cross sections of 3.0, 0.3, and 0.05 Å2 for collisional excitation transfer from Hg(63P1) to the 82S1/2, 62D, and 72S1/2 states in thallium, respectively. The results are fully consistent with previously determined cross sections for excitation transfer in other binary metallic vapor systems.

SENSITIZED FLUORESCENCE IN VAPORS OF ALKALI METALS: VIII. ENERGY TRANSFER BETWEEN THE 4 2P LEVELS IN POTASSIUM INDUCED BY INELASTIC COLLISIONS

1966 ◽  
Vol 44 (4) ◽  
pp. 753-768 ◽  
Author(s):  
G. D. Chapman ◽  
L. Krause
Keyword(s):  
Cross Sections ◽  
Alkali Metals ◽  
Inelastic Collisions ◽  
Inert Gases ◽  
Inert Gas ◽  
Vapor Pressures ◽  
Sensitized Fluorescence ◽  
Potassium Vapor ◽  
The Cross ◽  
Scattering Cross Sections

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.

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