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Journal of Physics B Atomic and Molecular Physics

Fine-structure mixing of Hg 6s6d states by collisions with ground-state Hg and Ar atoms, and N2molecules

R. J. Niefer, Murray R. Darrach, J. B. Atkinson, L. Krause

Published Feb 14, 1987• 6 citations
Publisher

Abstract

Excitation transfer between 6s6d Hg fine-structure states, induced by collisions with Hg, Ar and N 2 , was studied using methods of fluorescence spectroscopy in a vapour cell. Hg vapour, pure or mixed with Ar or N 2 , was excited to the 6 1 D 2 or 6 3 D 2 state by two-photon absorption and the relative intensities of the fluorescence components emitted from the radiatively and collisionally populated states were determined using a monochromator and a photomultiplier. Measurements of the fluorescent intensity ratios in relation to the density of the collision partner yielded the total thermally averaged cross sections for the transfers 1 D 2 to 3 D 2 , 1 D 2 to 3 D 3 3 D 2 to 3 D 3 , and 3 D 2 to 1 D 2 , with Hg, Ar and N 2 as collision partners.

DOI
10.1088/0022-3700/20/3/015

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Physical Review A•May 1, 1982•13 citations
Excitation transfer between 6s6d Hg fine-structure states, induced by collisions with Hg, Ar and N 2 , was studied using methods of fluorescence spectroscopy in a vapour cell. Hg vapour, pure or mixed with Ar or N 2 , was excited to the 6 1 D 2 or 6 3 D 2 state by two-photon absorption and the relative intensities of the fluorescence components emitted from the radiatively and collisionally populated states were determined using a monochromator and a photomultiplier. Measurements of the fluorescent intensity ratios in relation to the density of the collision partner yielded the total thermally averaged cross sections for the transfers 1 D 2 to 3 D 2 , 1 D 2 to 3 D 3 3 D 2 to 3 D 3 , and 3 D 2 to 1 D 2 , with Hg, Ar and N 2 as collision partners.
Cross sections for 6^D, 7^D and 8^0 fine-structure mixing in Rb, induced in collisions with various ground-state atoms and N2 molecules, have been determined using methods of atomic fluorescence.Rb vapour, pure or mixed with a buffer gas, was irradiated in a glass fluorescence cell with pulses of radiation from a N2 laser-pumped dye laser, populating a fine-structure state by two-photon absorption.The resulting fluorescence included a direct component emitted in the decay of .the optically excited state and a sensitized component due to the col1isional1y populated fine-structure state.Measure ments of relative intensities of the two components in relation to buffer gas (or Rb vapour) pressure yielded the following cross sections.-14 2 Inelastic Cross sections (10 cm ) process Rb He Ne Ar Kr Xe I would like to express sincere thanks to Professor L.
Cross sections for 72D{7}^{2}D72D and 82D{8}^{2}D82D fine-structure mixing in Rb, induced by collisions with various ground-state atoms and N2{\mathrm{N}}_{2}N2​ molecules, have been determined using methods of atomic fluorescence. Rb vapor, pure or mixed with a buffer gas, was irradiated in a glass fluorescence cell with pulses of radiation from a N2{\mathrm{N}}_{2}N2​ laser-pumped dye laser, populating a 2D^{2}D2D fine-structure state by two-photon absorption. The resulting fluorescence included a direct component arising from the optically excited state and a sensitized component due to the collisionally populated fine-structure state. Measurements of relative intensities of the two components in relation to buffer-gas pressure yielded the following cross sections (in units of ${10}^{\ensuremath{-}14}$ cm2{\mathrm{cm}}^{2}cm2): $Q({7}^{2}{D}_{\frac{3}{2}}\ensuremath{\rightarrow}{7}^{2}{D}_{\frac{5}{2}})=14.1,15.5,\mathrm{and}10.0$; $Q({7}^{2}{D}_{\frac{3}{2}}\ensuremath{\leftarrow}{7}^{2}{D}_{\frac{5}{2}})=9.0,10.5,\mathrm{and}6.9$, for Kr, Xe, and N2{\mathrm{N}}_{2}N2​, respectively; $Q({8}^{2}{D}_{\frac{3}{2}}\ensuremath{\rightarrow}{8}^{2}{D}_{\frac{5}{2}})=8.9,4.9,12.4,24.9,25.8,12.1,\mathrm{and}43.1$; $Q({8}^{2}{D}_{\frac{3}{2}}\ensuremath{\leftarrow}{8}^{2}{D}_{\frac{5}{2}})=5.8,3.2,9.4,15.1,17.6,8.3,\mathrm{and}28.5$, for He, Ne, Ar, Kr, Xe, N2{\mathrm{N}}_{2}N2​, and Rb, respectively. Cross sections for the effective depopulation of the 2D^{2}D2D states were also determined.
Cross sections for inelastic transfer between the 82D3/2 and 82D5/2 fine-structure states in rubidium, induced in resonant collisions with ground-state Rb atoms, have been determined using an experimental method involving two-photon excitation of atomic fluorescence. Rubidium vapor in a fluorescence cell was irradiated with pulses of 641 nm radiation from a N2 laser-pumped dye-laser tuned to excite one of the 82D states. The resulting fluorescence included the direct component originating from the optically excited state and a sensitized component arising from the other fine-structure state populated by collisions. Relative intensities of the fluorescent components, determined by photon-counting techniques, yielded the cross sections for excitation transfer: Q(2D3/2 → 2D5/2) = 8.1 × 10−13 cm2; Q(2D3/2 ← 2D5/2) = 5.5 × 1013 cm2; as well as [Formula: see text], the effective quenching cross section. The excitation transfer cross sections which are considered accurate to within ±20% are in the ratio predicted by the principle of detailed balancing.
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.
Rb atoms were excited to the 5P3/2 level using a single-mode laser diode. The 5P3/2 state atom density was measured by the absorption of line from a Rb hollow-cathode lamp. The excited atom density is combined with measured fluorescence ratio to determine collisional cross section for the energy pooling process [i.e. Rb(5P3/2)+Rb(5P3/2)→Rb(5D)+Rb(5S)]. The cross section is (5.0±1.9)(?)10-14cm2. Cross section for 5P3/2 →5P1/2 transfer in Rb, induced in collision with ground-state Rb atoms, has been determined using methods of atomic fluorescence. The resulting fluorescence included a direct component arising from the optically excited state and a sensitized component due to the collisionally populated fine-structure state and the energy-pooling collisions. Measurement of relative intensities of the two components yielded the following cross section: σ(5P3/2→5P1/2)=(3.0±0.9)×10-15cm2. It is found that the rate for the energy pooling is an order of magnitude more efficient than 5P3/2→5P1/2 mixture. Comparisons of our result with other experiments have been made.
Cross sections for $7^{2}D_{\frac{3}{2}}\ensuremath{\leftrightarrow}7^{2}D_{\frac{5}{2}}$ transfer in Rb, induced in collisions with He, Ne, Ar, and with ground-state Rb atoms, have been determined using methods of atomic fluorescence. Rb vapor, pure or mixed with a noble gas, was irradiated in a glass fluorescence cell with pulses of 660-nm radiation from a N2{\mathrm{N}}_{2}N2​-laser-pumped dye laser, populating one of the 2D^{2}D2D states by two-photon absorption. The resulting fluorescence included a direct component emitted in the decay of the optically excited state and a sensitized component arising from the collisionally populated state. Relative intensities of the components yielded the cross sections for 72D7^{2}D72D mixing: $Q(^{2}D_{\frac{3}{2}}\ensuremath{\rightarrow}^{2}D_{\frac{5}{2}})=8.8,6.5,10.4, \mathrm{and} 30$; $Q(^{2}D_{\frac{3}{2}}\ensuremath{\leftarrow}^{2}D_{\frac{5}{2}})=5.8,4.0,6.9, \mathrm{and} 18$, in units of ${10}^{\ensuremath{-}14}$ cm2{\mathrm{cm}}^{2}cm2 for He, Ne, Ar, and Rb, respectively. Cross sections for the effective quenching of the 2D^{2}D2D states were also determined.