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

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.

1978 ◽  
Vol 56 (7) ◽  
pp. 891-896 ◽  
Author(s):  
M. K. Wade ◽  
M. Czajkowski ◽  
L. Krause

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.


1968 ◽  
Vol 46 (19) ◽  
pp. 2127-2131 ◽  
Author(s):  
M. Stupavsky ◽  
L. Krause

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.


1973 ◽  
Vol 51 (3) ◽  
pp. 257-265 ◽  
Author(s):  
I. N. Siara ◽  
L. Krause

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.


1968 ◽  
Vol 46 (9) ◽  
pp. 1051-1057 ◽  
Author(s):  
D. A. McGillis ◽  
L. Krause

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.


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.


1973 ◽  
Vol 51 (14) ◽  
pp. 1582-1589 ◽  
Author(s):  
M. Czajkowski ◽  
L. Krause ◽  
G. M. Skardis

The behavior of the sensitized fluorescent spectrum of sodium, produced by irradiating Hg–Na–N2 mixtures with Hg 2537 Å resonance radiation, was studied in relation to N2 pressure. In this ternary vapor-gas system, the sodium atoms become excited by collisional transfer from Hg 63P1 atoms and also from Hg 63P0 atoms which are formed in Hg(63P1) + N2 collisions. The spontaneous decay of the collisionally populated S, P, and D sodium states gives rise to the fluorescent spectrum and their radiationless decay (quenching) caused by collisions with N2 molecules, manifests itself in a decrease of the fluorescent intensities as N2 pressure is increased. An analysis of the variation of the fluorescent intensities with N2 pressure, yielded 15 quenching cross sections for various S, P, and D sodium states, which appear to exhibit resonance properties with respect to upward vibrational transitions in N2.


1974 ◽  
Vol 52 (22) ◽  
pp. 2228-2234 ◽  
Author(s):  
M. Czajkowski ◽  
L. Krause

The transfer of excitation energy induced in inelastic collisions between excited Hg atoms and ground-state Cd atoms was studied using methods of sensitized fluorescence. Hg atoms in a low-density Hg–Cd vapor mixture were excited with Hg 2537 Å resonance radiation to the 63P1 state and interacted with the Cd atoms which became collisionally excited to the 53P1 state and subsequently decayed emitting sensitized fluorescence. Measurements of relative intensities of Hg 2537 Å resonance fluorescence and Cd 3261 Å sensitized fluorescence yielded the cross section Q(63P1 → 53P1) = 4.6 × 10−2 Å2. The efficiency of the excitation transfer was enhanced by the addition of small quantities of N2 to the Hg–Cd system. The cross section for quenching of the Cd 53P1 state by collisions with N2 was found to be 1.7 Å2.


1976 ◽  
Vol 54 (5) ◽  
pp. 603-610 ◽  
Author(s):  
M. Czajkowski ◽  
L. Krause

The transfer of excitation energy, induced in inelastic collisions between excited Hg atoms and ground state Zn atoms, was studied using methods of sensitized fluorescence. Hg atoms in a low density Hg–Zn mixture were excited with Hg 2537 Å resonance radiation to the 63P1 state, and interacted with the Zn atoms which became collisionally excited to the 43P1 state and then decayed emitting sensitized fluorescence. Measurements of relative intensities of Hg 2537 Å resonance fluorescence and Zn 3076 Å sensitized fluorescence yielded the cross section of 5.9 × 10−2 Å2 for Hg(63P1) → Zn(43P1) excitation transfer. The addition of small quantities of N2 to the Hg–Zn vapor mixture enhanced the efficiency of the transfer. The cross section for quenching of the Zn 43P1 state by collisions with N2 was found to be 0.19 Å2.


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.


1970 ◽  
Vol 48 (22) ◽  
pp. 2761-2768 ◽  
Author(s):  
E. S. Hrycyshyn ◽  
L. Krause

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.


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