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Proceedings of the National Academy of Sciences

The Metastable 2 p 3 -State of Mercury Atoms

S. Loria

Published Nov 1, 1925• 3 citations
Publisher

Abstract

Let us consider a mixture of mercury vapor, thallium vapor and nitrogen in a closed quartz tube under well defined conditions of pressure and temperature, illuminated by λ 2537A of constant intensity. \n \nDue to the absorption of the illuminating radiation a constant number N of mercury atoms will be activated in unit time. Those activated atoms persist in the 2p2-state for a finite time t which is known to be of the order of magnitude of 10^-7 sec [1]. If they escape collision during this period they return to their normal state in the ordinary wave-emitting radiation (resonance). They may, however, while activated, collide with nitrogen molecules, normal mercury atoms or normal thallium atoms. We shall assume, for the present, that the amount of nitrogen and thallium sufficiently exceeds the amount of mercury, so that we may disregard totally the collisions between activated and normal mercury atoms. \n \nWe assume furthermore that all collisions between activated mercury atoms and thallium atoms result in the activation of the latter, producing the fluorescence radiation of thallium with a constant energy distribution between its different lines.

DOI
10.1073/pnas.11.11.673

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Measurement of the Life of the Metastable Mercury Atom

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Half value time for the ${2}^{3}$${\mathrm{P}}_{0}$ state of Hg for various pressures of admixed ${\mathrm{N}}_{2}$--- 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 $2^{3}P_{0}$ 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.

Physical Review•Jan 1, 1929•14 citations

Controlled orbital transfers of electrons in optically excited mercury atoms

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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.

Proceedings of the Royal Society of London Series A Containing Papers of a Mathematical and Physical Character•Dec 1, 1924•28 citations

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

C. G. Matland

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.

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Stepwise Fluorescence in Mercury-Nitrogen Mixtures The 3650 Line

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On Life and Concentration of Metastable Atoms and the Quenching of Mercury Resonance Radiation

Enrique Gaviola

A complete and general study of the dependence of life and concentration of metastable mercury atoms, optically excited, on experimental conditions, on foreign gas-pressures, and on intensity of illumination is given. This study explains why the life can not be larger than ${10}^{\ensuremath{-}2}$ second under laboratory conditions and why foreign gases act so differently in regard to the accumulation of excited atoms. The theoretical results are in good agreement with all experimental data available. An improved and more general formula for the quenching of mercury resonance radiation is obtained. The efficiencies of collisions of the second kind of metastable mercury atoms with ${\mathrm{N}}_{2}$, A, and He molecules are calculated numerically. It is shown that the concentration of metastable atoms increases only with the square root of the intensity of the exciting light and not with the exciting light itself as generally assumed.

Physical Review•Nov 15, 1929•12 citations

The Metastable State in Mercury Vapor

Harold W. Webb

Metastable state produced in mercury vapor at low pressures by electron impacts of 4.9 volts.---The persistence of the "radiation" produced by 4.9 volt impacts in mercury vapor was measured in a four electrode tube of the type usually employed in resonance potential measurements, consisting of an equipotential cathode of simple design, an inner grid $G$ for controlling the velocity of the impacting electrons, an outer photo-electric grid $H$ and a photo-electric plate $P$. A.c. and d.c. voltages were applied to the two grids in such a way that the electrons had sufficient velocity to excite the radiation only in alternate half-cycles and that the photo-electric current to the electrometer alternated in direction simultaneously. As a result of the persistence of the radiation there resulted a decrease in the current with increasing frequency, reaching a minimum at 1800 cycles for a distance between grids of 17 mm and at 3800 cycles for a distance of 8.5 mm. These results did not vary much with pressure,.003 to.032 mm. They show a lapse of time between the excitation and the arrival of the first radiation at the plate $P$ of about 1/3600 and 1/7600 sec. respectively. A mathematical discussion shows that the diffusion of the radiation by repeated emission and re-absorption (the "imprisonment" of radiation theory) cannot account for these results. A calculation, based on the assumption that the excited atoms remain in a metastable state and carry the energy of excitation to the photo-electric surfaces and there give it up, gives results in very close agreement with the observations. The conclusion is that a metastable state is formed by the atoms excited by the 4.9 volt electron impacts and that these are the effective ones in producing the photo-electric response in the tubes. In these experiments the $2{p}_{2}$ state is the only one excited by the impacts in appreciable amount. How these results can be reconciled with the Bohr theory, according to which the $2{p}_{2}$ state is not metastable, is not clear.

Physical Review•Aug 1, 1924•62 citations
Let us consider a mixture of mercury vapor, thallium vapor and nitrogen in a closed quartz tube under well defined conditions of pressure and temperature, illuminated by λ 2537A of constant intensity. \n \nDue to the absorption of the illuminating radiation a constant number N of mercury atoms will be activated in unit time. Those activated atoms persist in the 2p2-state for a finite time t which is known to be of the order of magnitude of 10^-7 sec [1]. If they escape collision during this period they return to their normal state in the ordinary wave-emitting radiation (resonance). They may, however, while activated, collide with nitrogen molecules, normal mercury atoms or normal thallium atoms. We shall assume, for the present, that the amount of nitrogen and thallium sufficiently exceeds the amount of mercury, so that we may disregard totally the collisions between activated and normal mercury atoms. \n \nWe assume furthermore that all collisions between activated mercury atoms and thallium atoms result in the activation of the latter, producing the fluorescence radiation of thallium with a constant energy distribution between its different lines.
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.
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.
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.
The experiments of Wood and of Gaviola show that when mercury vapor is illuminated by light from a mercury arc, and nitrogen is added in increasing amounts, the concentration of atoms in the 3P2^{3}P_{2}3P2​ state passes through a minimum. No simple theory accounts for this result. An explanation involving excitation of atoms in the 3P1^{3}P_{1}3P1​ state by vibrating nitrogen molecules is discussed. The results obtained when a filter of bromine vapor is used indicate a transfer of excited mercury atoms from one to another 3D^{3}D3D state upon collision with nitrogen.
A complete and general study of the dependence of life and concentration of metastable mercury atoms, optically excited, on experimental conditions, on foreign gas-pressures, and on intensity of illumination is given. This study explains why the life can not be larger than ${10}^{\ensuremath{-}2}$ second under laboratory conditions and why foreign gases act so differently in regard to the accumulation of excited atoms. The theoretical results are in good agreement with all experimental data available. An improved and more general formula for the quenching of mercury resonance radiation is obtained. The efficiencies of collisions of the second kind of metastable mercury atoms with N2{\mathrm{N}}_{2}N2​, A, and He molecules are calculated numerically. It is shown that the concentration of metastable atoms increases only with the square root of the intensity of the exciting light and not with the exciting light itself as generally assumed.
Metastable state produced in mercury vapor at low pressures by electron impacts of 4.9 volts.---The persistence of the "radiation" produced by 4.9 volt impacts in mercury vapor was measured in a four electrode tube of the type usually employed in resonance potential measurements, consisting of an equipotential cathode of simple design, an inner grid GGG for controlling the velocity of the impacting electrons, an outer photo-electric grid HHH and a photo-electric plate PPP. A.c. and d.c. voltages were applied to the two grids in such a way that the electrons had sufficient velocity to excite the radiation only in alternate half-cycles and that the photo-electric current to the electrometer alternated in direction simultaneously. As a result of the persistence of the radiation there resulted a decrease in the current with increasing frequency, reaching a minimum at 1800 cycles for a distance between grids of 17 mm and at 3800 cycles for a distance of 8.5 mm. These results did not vary much with pressure,.003 to.032 mm. They show a lapse of time between the excitation and the arrival of the first radiation at the plate PPP of about 1/3600 and 1/7600 sec. respectively. A mathematical discussion shows that the diffusion of the radiation by repeated emission and re-absorption (the "imprisonment" of radiation theory) cannot account for these results. A calculation, based on the assumption that the excited atoms remain in a metastable state and carry the energy of excitation to the photo-electric surfaces and there give it up, gives results in very close agreement with the observations. The conclusion is that a metastable state is formed by the atoms excited by the 4.9 volt electron impacts and that these are the effective ones in producing the photo-electric response in the tubes. In these experiments the 2p22{p}_{2}2p2​ state is the only one excited by the impacts in appreciable amount. How these results can be reconciled with the Bohr theory, according to which the 2p22{p}_{2}2p2​ state is not metastable, is not clear.