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Canadian Journal of Physics

Quenching of Mercury-Sensitized Fluorescence in Sodium, Induced in Collisions with N2 Molecules

M. Czajkowski, L. Krause, George M. Skardis

Published Jul 15, 1973• 10 citations
Publisher

Abstract

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.

DOI
10.1139/p73-209

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

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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.

Canadian Journal of Physics•Feb 1, 1973•12 citations

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

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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.

Canadian Journal of Physics•Oct 1, 1968•23 citations

Sensitized fluorescence in zinc, induced in collisions with excited Hg atoms

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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.

Canadian Journal of Physics•Mar 1, 1976•12 citations

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

Murray 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.

Canadian Journal of Physics•Jul 1, 1978•10 citations

Sensitized Fluorescence in Cadmium Induced in Collisions with Excited Hg Atoms

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.

Canadian Journal of Physics•Nov 15, 1974•12 citations

Inelastic Collisions between Excited Alkali Atoms and Molecules. II. The Quenching of Sodium Resonance Radiation by N2 , H2 , HD, and D2

B P Kibble, G. H. Copley, L. Krause

The cross sections for quenching collisions between excited sodium atoms and ${\mathrm{N}}_{2}$, ${\mathrm{H}}_{2}$, HD, and ${\mathrm{D}}_{2}$ molecules in their electronic ground states have been determined using a delayed-coincidence method. The sodium atoms in mixtures with the gases were excited with 20-nsec pulses of NaD radiation, and the delays between the exciting and fluorescent pulses were measured with a time-to-pulse-height converter. The resulting pulse-height spectra, which were accummulated in a 400-channel kicksorter, yielded the effective lifetimes ${\ensuremath{\tau}}^{\ensuremath{'}}$ of the sodium resonance state, which are shorter than the natural lifetime $\ensuremath{\tau}$ because of the nonradiative decay induced in collisions with the molecules. The cross sections for collisions with ${\mathrm{N}}_{2}$, ${\mathrm{H}}_{2}$, HD, and ${\mathrm{D}}_{2}$, obtained from an analysis of the dependence of ${\ensuremath{\tau}}^{\ensuremath{'}}$ on the gas pressures, are 30.4\ifmmode\pm\else\textpm\fi{}1.2, 16.2\ifmmode\pm\else\textpm\fi{}0.3, 11.6\ifmmode\pm\else\textpm\fi{}0.4, and 9.8\ifmmode\pm\else\textpm\fi{}0.3 ${\mathrm{\AA{}}}^{2}$, respectively.

Physical Review•Jul 5, 1967•48 citations
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.
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.
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.
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.
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.
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.
The cross sections for quenching collisions between excited sodium atoms and N2{\mathrm{N}}_{2}N2​, H2{\mathrm{H}}_{2}H2​, HD, and D2{\mathrm{D}}_{2}D2​ molecules in their electronic ground states have been determined using a delayed-coincidence method. The sodium atoms in mixtures with the gases were excited with 20-nsec pulses of NaD radiation, and the delays between the exciting and fluorescent pulses were measured with a time-to-pulse-height converter. The resulting pulse-height spectra, which were accummulated in a 400-channel kicksorter, yielded the effective lifetimes ${\ensuremath{\tau}}^{\ensuremath{'}}$ of the sodium resonance state, which are shorter than the natural lifetime $\ensuremath{\tau}$ because of the nonradiative decay induced in collisions with the molecules. The cross sections for collisions with N2{\mathrm{N}}_{2}N2​, H2{\mathrm{H}}_{2}H2​, HD, and D2{\mathrm{D}}_{2}D2​, obtained from an analysis of the dependence of ${\ensuremath{\tau}}^{\ensuremath{'}}$ on the gas pressures, are 30.4\ifmmode\pm\else\textpm\fi{}1.2, 16.2\ifmmode\pm\else\textpm\fi{}0.3, 11.6\ifmmode\pm\else\textpm\fi{}0.4, and 9.8\ifmmode\pm\else\textpm\fi{}0.3 A˚2{\mathrm{\AA{}}}^{2}A˚2, respectively.