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Physical Review

Hyperfine Structure Absorption in Optically Excited Mercury Vapor

M. L. Pool, S. J. Simmons

Published Dec 15, 1933• 1 citation
Publisher

Abstract

The radiation 4047, 2967 and 2752, all terminating on the $2^{3}P_{0}$ state of mercury, was passed through optically excited mercury vapor and the absorption of each wavelength for various lengths of excited vapor and for various pressures of admixed nitrogen was measured photometrically. With low dispersion the intensity of 2752 decreased nearly exponentially with increase in length of excited vapor giving a constant linear absorption coefficient. But the lines 4047 and 2967 were found not to obey the exponential law, the fractional decrease in intensity per unit length of path decreased rapidly as the total length of the absorbing vapor increased. With high dispersion the absorption of the five components of 4047 was strong and increased with increase of admixed nitrogen. The strongest component showed the strongest absorption and the amount of absorption decreased with decrease in intensity of components. The intensity of each component decreased nearly exponentially with increase in length of excited mercury vapor. Both components of 2967 showed strong absorption. None of the components of 4358 or 5461 showed measurable absorption.

DOI
10.1103/physrev.44.997

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The Quenching of Mercury Resonance Radiation (2537A) by Nitrogen

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When a mercury atom in the resonance $6^{3}P_{1}$ state collides with a nitrogen molecule, it may be transferred to the metastable $6^{3}P_{0}$ state. The cross section for this reaction has been measured by a new method. Mercury vapor, in the presence of a known pressure of nitrogen gas, is excited by 2537A radiation. After the source of the excitation is cut off, the decay time of the imprisoned radiation is observed. The quenching collision cross section ${\ensuremath{\sigma}}_{Q}$ is calculated from the measured decay time and the known value of the imprisonment time in the absence of the quenching gas. Measurements have been taken over the temperature range 325-525\ifmmode^\circ\else\textdegree\fi{}K; ${\ensuremath{\sigma}}_{Q}$ is found to increase from 5.0\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}17}$ ${\mathrm{cm}}^{2}$ at the lower temperature to 1.0\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}16}$ ${\mathrm{cm}}^{2}$ at the upper temperature.

Physical Review•Nov 1, 1953•32 citations
The radiation 4047, 2967 and 2752, all terminating on the 23P02^{3}P_{0}23P0​ state of mercury, was passed through optically excited mercury vapor and the absorption of each wavelength for various lengths of excited vapor and for various pressures of admixed nitrogen was measured photometrically. With low dispersion the intensity of 2752 decreased nearly exponentially with increase in length of excited vapor giving a constant linear absorption coefficient. But the lines 4047 and 2967 were found not to obey the exponential law, the fractional decrease in intensity per unit length of path decreased rapidly as the total length of the absorbing vapor increased. With high dispersion the absorption of the five components of 4047 was strong and increased with increase of admixed nitrogen. The strongest component showed the strongest absorption and the amount of absorption decreased with decrease in intensity of components. The intensity of each component decreased nearly exponentially with increase in length of excited mercury vapor. Both components of 2967 showed strong absorption. None of the components of 4358 or 5461 showed measurable absorption.
Half value time for the 23{2}^{3}23P0{\mathrm{P}}_{0}P0​ state of Hg for various pressures of admixed N2{\mathrm{N}}_{2}N2​--- A high speed rotating disk has been used to interrupt the total radiation from a water-cooled and magnetically controlled quartz mercury arc before optically exciting mercury vapor in a quartz resonance tube at room temperature. In the neighborhood of ${10}^{\ensuremath{-}4}$ sec. after the optical excitation a flash of visible radiation from another water-cooled and magnetically controlled mercury arc was passed through the resonance tube and the absorption spectrum photographed. The line 4047 ($2^{3}P_{0}\ensuremath{-}2^{3}S_{1}$) showed strong absorption when a few millimeters of nitrogen were introduced into the resonance tube. The lines 4077, 4358, 5461, 5770 and 5790 showed no measurable absorption under similar conditions. The rate of decay of the amount of 4047 absorbed with respect to the time-wait after excitation of the mercury vapor was taken as the rate of decay of the metastable 23P02^{3}P_{0}23P0​ state. The life or half-value time of the state was found to vary markedly with the pressure of admixed nitrogen. The maximum life 4.2\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}4}$ sec. occurred for 6.8 mm of nitrogen. No absorption of 4047 was observed upon the introduction of hydrogen, argon, neon, or helium into the resonance tube.
The absorption of the resonance radiation (2536A) of mercury was studied by dividing the radiation from a resonance lamp into two parts, each part going into a separate photo-electric cell. An absorption cell containing mercury vapor whose pressure could be controlled by cooling a side tube was placed in the path of one beam. The ratio of the amount of light passing into each beam could be varied by a mechanical device. From the setting of the mechanical device, giving a balance between the two photo-electric currents, the absorption of the mercury vapor could be inferred. The absorption per atom was calculated and found to decrease rapidly as the total amount of absorbing vapor was increased, thus showing that the resonance radiation is not homogeneous. The maximum atomic absorption coefficient was 11\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}14}$, which indicates that an atom can stop the radiation which falls upon an area one hundred times larger than its cross sectional area.
Effect of nitrogen and of mixtures of nitrogen and carbon dioxide upon the fluorescence of mercury vapor. By "stepwise" optical excitation, unexcited mercury atoms are raised to the 23S12^{3}S_{1}23S1​ state. They may leave this level upon the emission of radiation by four paths---the first to the 21P12^{1}P_{1}21P1​ state, a transition of relatively low probability, and the other three to the 23P22^{3}P_{2}23P2​, 23P12^{3}P_{1}23P1​, and 23P02^{3}P_{0}23P0​ states with the emission of 5461A, 4358A and 4046A, respectively. Measurements, by totally independent methods, of the mean life of the 23S12^{3}S_{1}23S1​ state yielded values, when measured by the line 5461A, equal to approximately four times those when measured by either 4358A or 4046A. Upon the addition of foreign gas, then, the intensity ratio of 5461A to either 4358A or 4046A should decrease with increasing pressure while that of 4046A to 4358A should remain constant. However, these ratios were all found to be invariant with pressure, up to 400 mm in the case of nitrogen and up to 100 mm in the case of the nitrogen-carbon dioxide mixtures.
The theories of absorption in mercury vapor of mercury resonance light of wave-length 2536.7A as formulated by Malinowski and H. A. Wilson are briefly reviewed. It is well established that the absorption coefficient for resonance radiation increases as the number of absorbing atoms decreases. This is probably due to a Doppler effect in the radiating vapor. To diminish the influence of the Doppler effect a jet of mercury vapor was used, and the resonance radiation coming from it was investigated. A series of measurements of the absorption coefficient of this light is given. The maximum atomic absorption coefficient observed is 10.22\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}13}$, nine times as large as any previously observed. It is shown that Malinowski's assumptions are not in accord with the observed effects.
The mean life of the mercury line $\ensuremath{\lambda}2537$ was measured by the alternating voltage method previously described by Webb. The radiation was excited in a quartz tube by impact with electrons from a hot cathode. The photoelectric system was contained in a separate tube also of quartz. The photoelectric surface was zinc evaporated on a nickel plate. Measurements of the apparent life were made with diminishing mercury vapor pressures until further reduction of pressure produced no change in the measured rate of decay of the radiation. At these low pressures (below 3\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}4}$ mm, for the geometry used) the absorption and reemission of the radiation was negligible and the true life of a single excitation process was measured. This was found to be 1.08\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}7}$ sec. with an estimated precision of one percent.Absorption coefficient of $\ensuremath{\lambda}1849$. An absorption cell with a one mm thick absorbing layer of mercury vapor was mounted so as to move in and out between the excitation and photoelectric tubes used in the above measurements. The absorption of $\ensuremath{\lambda}1849$ was measured at pressures such that the absorption of $\ensuremath{\lambda}2537$ was negligible. From this the atomic absorption coefficient for the main component of the line was found to be 6.2\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}11}$ from which the mean life of the 21P12^{1}P_{1}21P1​ state was calculated to be 2.9\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}10}$ sec. with an estimated precision of 25 percent.
When a mercury atom in the resonance 63P16^{3}P_{1}63P1​ state collides with a nitrogen molecule, it may be transferred to the metastable 63P06^{3}P_{0}63P0​ state. The cross section for this reaction has been measured by a new method. Mercury vapor, in the presence of a known pressure of nitrogen gas, is excited by 2537A radiation. After the source of the excitation is cut off, the decay time of the imprisoned radiation is observed. The quenching collision cross section ${\ensuremath{\sigma}}_{Q}$ is calculated from the measured decay time and the known value of the imprisonment time in the absence of the quenching gas. Measurements have been taken over the temperature range 325-525\ifmmode^\circ\else\textdegree\fi{}K; ${\ensuremath{\sigma}}_{Q}$ is found to increase from 5.0\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}17}$ cm2{\mathrm{cm}}^{2}cm2 at the lower temperature to 1.0\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}16}$ cm2{\mathrm{cm}}^{2}cm2 at the upper temperature.