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Journal of Applied Physics

Rate Analysis of Multiple-Step Excitation in Mercury Vapor

Ralph Zito

Published May 1, 1963• 14 citations
Publisher

Abstract

In the course of studying a multiple-step excitation process in mercury vapor for the possible application to a three-dimensional display of data, an analysis of the fluorescence mechanism was made. A dual optical-excitation process is employed by which mercury vapor is caused to radiate at a localized region in space. The radiation is in the ultraviolet and visible portions of the spectrum. A partial analysis and pertinent literature review is presented here for the resonance absorption and reradiation of light energy by mercury vapor at room temperature.

DOI
10.1063/1.1729674

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Abstract As I have shown in numerous publications, the vapour of mercury in vacuo, even at temperatures below the solidifying point of the metal, when illuminated by the light of a water-cooled quartz mercury lamp, emits the monochromatic radiation of wave-length 2536. According to Bohr’s theory, this resonance radiation results from the fall of an electron from the 2p2 orbit, to which it has been raised from the IS orbit by the absorption of one quantum of 2536 radiation, back to the IS orbit, the orbit occupied by the electron when the atom is in its normal state. An atom in which the electron has been brought to the 2p2 orbit is in a condition to absorb the radiation of any other line produced by the fall of electrons from outer orbits to orbit 2p2, and Fuchtbauer has shown, in an extremely interesting and important paper (‘Physik. Zeit.,’ 1920), that a large number of the arc lines of mercury are radiated by cold mercury vapour illuminated by the mercury arc. He showed that, if the 2536 radiation was screened off by glass, none of the other lines appeared, and explained their presence as the result of the absorption by excited atoms with electrons at the 2p2 level, of the radiations terminating at this level, by which the electrons are carried out to other-orbits, from which they can fall back in various ways, giving rise to emission lines in the process. Though Fuchtbauer‘s experiment did not prove that this process actually took place, his explanation was the only one possible on modern theory, and the experiments which are to be considered in the present paper show that it was correct. Twenty years ago the most that could have been said would have been that the absorption of the 2536 radiation “shook” the atom in some way, causing it to emit its other frequencies as a sort of fluorescence, since Fuchtbauer’s experiment did not show that excitation by lines other than the 2536 line was necessary for the emission of the arc spectrum. To demonstrate experimentally that the step-by-step transfer of electrons from orbit to orbit actually takes place, it is necessary to illuminate the mercury vapour with various combinations of monochromatic light, and study the resultant emission spectrum.

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Experimental Determination of the De-excitation Cross Section for the 6P13 State of Mercury by Thallium

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Rate analysis of multiple-step excitation in mercury vapor

Vacuum•Jan 1, 1964•0 citations
In the course of studying a multiple-step excitation process in mercury vapor for the possible application to a three-dimensional display of data, an analysis of the fluorescence mechanism was made. A dual optical-excitation process is employed by which mercury vapor is caused to radiate at a localized region in space. The radiation is in the ultraviolet and visible portions of the spectrum. A partial analysis and pertinent literature review is presented here for the resonance absorption and reradiation of light energy by mercury vapor at room temperature.
Empirical data are presented for the preliminary intensity and resolution measurements made in the multiple-step induced fluorescence of mercury vapor. The primary application contemplated for such a process is the production of an isolated source of visible radiation in three-dimensional space. A dual optical excitation process is employed in conjunction with inelastic foreign gas molecule collision for the resultant spontaneous, visible fluorescence of excited mercury atoms. Details of the experimental apparatus and techniques employed are also given.
Empirical data are presented for the preliminary intensity and resolution measurements made in the multiple-step induced fluorescencof mercury vapor. The primary contemplated application for such a process is the production of an isolated source of visible radiation in three-dimensional space. A dual optical excitation process is employed in conjunction with inelastic foreign gas molecule collision for the resultant spontaneous, visible fluorescence of excited mercury atoms. Details of the experimental apparatus and techniques employed are also given. (Author)
Abstract As I have shown in numerous publications, the vapour of mercury in vacuo, even at temperatures below the solidifying point of the metal, when illuminated by the light of a water-cooled quartz mercury lamp, emits the monochromatic radiation of wave-length 2536. According to Bohr’s theory, this resonance radiation results from the fall of an electron from the 2p2 orbit, to which it has been raised from the IS orbit by the absorption of one quantum of 2536 radiation, back to the IS orbit, the orbit occupied by the electron when the atom is in its normal state. An atom in which the electron has been brought to the 2p2 orbit is in a condition to absorb the radiation of any other line produced by the fall of electrons from outer orbits to orbit 2p2, and Fuchtbauer has shown, in an extremely interesting and important paper (‘Physik. Zeit.,’ 1920), that a large number of the arc lines of mercury are radiated by cold mercury vapour illuminated by the mercury arc. He showed that, if the 2536 radiation was screened off by glass, none of the other lines appeared, and explained their presence as the result of the absorption by excited atoms with electrons at the 2p2 level, of the radiations terminating at this level, by which the electrons are carried out to other-orbits, from which they can fall back in various ways, giving rise to emission lines in the process. Though Fuchtbauer‘s experiment did not prove that this process actually took place, his explanation was the only one possible on modern theory, and the experiments which are to be considered in the present paper show that it was correct. Twenty years ago the most that could have been said would have been that the absorption of the 2536 radiation “shook” the atom in some way, causing it to emit its other frequencies as a sort of fluorescence, since Fuchtbauer’s experiment did not show that excitation by lines other than the 2536 line was necessary for the emission of the arc spectrum. To demonstrate experimentally that the step-by-step transfer of electrons from orbit to orbit actually takes place, it is necessary to illuminate the mercury vapour with various combinations of monochromatic light, and study the resultant emission spectrum.
The de-excitation or quenching cross section of thallium for the 63P16^{3}P_{1}63P1​ state of mercury has been obtained over a range of temperatures of 800 to 900\ifmmode^\circ\else\textdegree\fi{}C. Comparison of the resonance fluorescence from a mercury-thallium vapor mixture with the resonance fluorescence from a pure mercury vapor at the same number density, as determined by line absorption, allows the calculation of the de-excitation cross section. The present data together with Garrett's value of the lifetime of the 63P16^{3}P_{1}63P1​ state of mercury and existing data on the vapor pressures of mercury and thallium were used to obtain values of the de-excitation cross section. Values of the cross section range from 108\ifmmode\pm\else\textpm\fi{}41 A˚2{\mathrm{\AA{}}}^{2}A˚2 at 800\ifmmode^\circ\else\textdegree\fi{}C to 80\ifmmode\pm\else\textpm\fi{}19 A˚2{\mathrm{\AA{}}}^{2}A˚2 at 900\ifmmode^\circ\else\textdegree\fi{}C. The corresponding quenching-rate coefficients varied from (5.1\ifmmode\pm\else\textpm\fi{}1.9)\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}7}$ cm3{\mathrm{cm}}^{3}cm3/sec at 800\ifmmode^\circ\else\textdegree\fi{}C to (4.0\ifmmode\pm\else\textpm\fi{}0.9)\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}7}$ cm3{\mathrm{cm}}^{3}cm3/sec at 900\ifmmode^\circ\else\textdegree\fi{}C.
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.