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Proceedings of the Royal Society of London Series A Containing Papers of a Mathematical and Physical Character

On the fluorescence and channelled absorption spectra of cæsium and other alkali elements

John Cunningham McLennan, Donald S. Ainslie

Published May 3, 1923• 8 citations
Publisher

Abstract

Abstract In 1874 it was shown by Roscoe and Schuster that channelled absorption spectra can be obtained with the vapours of the alkali elements sodium and potassium, and later on these spectra were investigated in some detail by Liveing and Dewar. It was also shown in 1896 by Weidemann and Schmidt that the vapours of these same metals emitted a radiation possessing characteristics of a fluorescence spectrum when they were traversed by white light. Since 1903 exhaustive studies have been made of both the fluorescence and the channelled absorption spectrum of sodium by R. W. Wood, together with a number of collaborators, Including J. H. Moore and F. E. Hackett. In these investigation it was shown that the channelled absorption spectrum of sodium was made up of a number of series of absorption bands, one set of series being on the red wave-length side of the D lines, and another lying in the visible blue-green region. In addition, series of absorption bands were found by them with approximately regular spacing in the neighbourhood of λ = 3303 A, the second member of the doublet series of this element. As regards the fluorescence spectrum of sodium, they found that, by stimulation of the vapour with approximately monochromatic light, there resulted an emission of light, the spectrum of which consisted of a number of bright but narrow bands of varying intensity, more or less regularly spaced both above and below the mean wave-length of the exciting light. They observed, too, that the slightest change in the wave-length of the exciting light resulted in the disappearance of one set of lines and in the appearance of another of different wave-lengths. In the various florescence spectra obtained by R. W. Wood when stimulating sodium vapour by monochromatic light from different sources, it was noted that there was a remarkable recurrence of the interval, ∆λ = 52·3 A. in the spacing of the fluorescence bands.

DOI
10.1098/rspa.1923.0058

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Observations on the fluorescence and resonance of sodium vapour.—II

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Abstract Prof. R. W. Wood has made many interesting observations on the fluorescence of sodium vapour. They are conveniently summarised in his ‘Physical Optics’ (MacMillan, 1911). The fluorescent spectra he has obtained are apparently connected with the banded absorption spectrum of dense sodium vapour. If white light is employed, this banded absorption spectrum is re-emitted completely as a fluorescent emission spectrum. If monochromatic light is used, a portion only of the complete band spectrum is emitted, this portion consisting of a moderate number of lines approximately equally spaced along a normal spectrum, and including a line coincident with the exciting line. These observations on the band spectrum are of great interest and importance, but observations on the line spectrum of sodium, in absorption and in fluorescence, are more within the range of theoretical discussion at the present time.

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Continuous absorption of light in cæsium vapour

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Abstract A region of continuous absorption lying on the short wave-length side of the limit of the principal series and corresponding to the photo-ionization of the atom is to be expected in the alkali metal vapours. The currents due to photo-ionization have been measured and several attempts have been made to observe the absorption. The main difficulty is in the action of the vapour on the windows of the absorption cell. This has usually been overcome by keeping the ends of the absorption tube cool and checking the diffusion of the vapour from the centre of the tube by means of a foreign gas. This gas produces a large and complicated effect on the absorption (Harrison). In the present experiments it has been found possible to avoid the use of a foreign gas by employing a long absorption tube and a low vapour pressure. Cæsium was used because it gives a sufficient pressure at a moderate temperature and because its series limit lies in the most convenient region of the spectrum.

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Fluorescent emission of the mercury line 2537 A at pressures between 10-3 and 10-1 mm

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Abstract In his first papers on the resonance radiation of mercury and sodium Wood describes how the character of the emission changes with increasing pressure of the fluorescent vapour. At low pressure (p = 10-3 mm) the emission comes wholly from a narrow well-defined beam corresponding to the path of the primary light (beam fluorescence). With increasing density of the vapour the beam becomes diffuse until the luminosity fills the whole volume (volume fluorescence) and finally at pressures of about 0·1 mm it withdraws entirely to the spot of entrance of the primary light (surface fluorescence). In all three cases the absorption and emission of light are due to normal atoms; the phenomenon is that of normal or true resonance radiation. For the D-lines of sodium, Lord Rayleigh showed as early as 1919 that, even at pressures at which the true resonance radiation is concentrated on the surface, an emission can in addition be observed within the volume along the path of the primary light, if the D-lines in the spectrum of the exciting source are not too narrow. This new fluorescence beam which can only be excited by the outer parts of the D-lines is partially polarized. Later Jablonsky and Pringsheim found that though the normal resonance radiation observed on the surface is unpolarized under these conditions, the degree of polarization of the new fluorescence beam can be as high as 30% and is practically unaltered by the action of a magnetic field. For the mercury resonance line 2537 A it was Rayleigh who again studied the phenomena at higher pressures but with his main interest concentrated on the duration of the processes and on the appearance of the well-known mercury bands. In his paper, the continuous change of the fluorescence in the vapour volume is studied from room temperature up to 200°C. He used as a source of excitation a “not fully cooled” mercury lamp, giving a somewhat broadened and partially self-reversed line at 2537 A, which produces the effect called by Rayleigh “core­ effect”. The latter is in Rayleigh’s terminology the fluorescence of mercury vapour produced by the more central part of the 2537 A line while the very different fluorescence emission which is excited by a much broadened and self-reversed line is called by him the wing effect. The core effect always shows a line which, with the available dispersion, seems to coincide with the resonance line itself; when the pressure increases, a number of bands appear which have no importance for the present paper. Since in saturated vapour at 100° C the normal resonance radiation has withdrawn to the surface, it is improbable that the core effect is produced by the most central region of the primary line by which the normal resonance radiation at the lowest pressures is excited.

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Robert William Ditchburn, P. J. Jutsum, Geoffrey V. Marr

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Dispersion of light by Potassium Vapour

P. V. Bevan

Abstract Anomalous dispersion in the region of the red lines of potassium was first observed by Ebert in 1904. The method adopted for Ebert’s experiments was a modified form of the crossed prism method used by Wood in the investigation of the corresponding phenomena in the case of sodium. Potassium was heated in a tube through which two currents of hydrogen passed from each end to a central outlet. The cool hydrogen kept the potassium vapour in a prismatic form, so that light passing along the length of the tube suffered deviation and dispersion by the potassium vapour prism. The author of the present communication has shown that there is no need for the hydrogen streams. If the tube be kept cool on its upper surface the metallic vapour takes of itself a prismatic form or is arranged in layers of decreasing density, and so behaves in a similar way to a prism of homogeneous vapour. The present communication deals with quantitative results from the measurement of dispersions at different wave-lengths, and it appears that the deviation due to potassium vapour is observable over the whole of the visible spectrum and for a considerable distance in the ultra-violet. Strong absorption takes place at the lines of the principal series and for wave-lengths near these series lines we have "anomalous" dispersion. This phenomenon has been observed at seven of the pairs forming the principal series lines for potassium—as the pairs of lines in this series get closer and closer together with diminishing wave-length, the dispersion effects after the first two pairs are only observable outside the lines forming a pair, but there appears a lack of symmetry in the observed dispersion curves corresponding to the different intensities of the lines forming the pair. The dispersion to be observed may then be regarded as that corresponding to the principal series absorption lines; no other absorption region seems to affect the dispersion —at any rate at low densities of vapour.

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Resonance Radiation of Sodium Vapor Excited by one of the D Lines

Robert Williams Wood, Fred L. Mohler

TPHE purpose of this investigation was to study the resonance spec--*-trum of sodium vapor when the resonance was excited by a single D line.In a paper on " Resonance Radiation of Sodium Vapor "* published by one of us in 1905, it was shown that if a bulb containing pure sodium vapor was illuminated by light from a sodium flame, the vapor emitted a yellow light which spectroscopic analysis showed to be identical with the exciting light, in other words, the two D lines.It was suggested at this time that it would be interesting to see if both D lines appeared when the vapor was illuminated by a single D line.This would determine whether the mechanisms that give rise to the D lines are separate or in some way connected.In 1914 this experiment was tried by Wood and Dunoyer. 2 This experiment was made possible by the discovery of a polarization method of separating close spectral doublets that eliminated the great loss of light involved in a high-power monochromator, but even with this method the resonance light is very faint.The spectrum of resonance excited by D 2 was photographed with exposures varying from 10 to 15 hours.The majority of the plates showed only the D 2 line, but owing to under exposure Di would not have been visible if it was less than one fourth of the intensity of D 2 .Some plates indeed showed both Di and D 2 , but the presence of Di in the exciting light was judged to be the cause of this.Imperfections in the optical system made it impossible to entirely remove Di from the exciting light and as it was sensitive to temperature changes the nature of the transmitted light sometimes changed during an exposure.It was concluded that sodium resonance excited by D 2 consisted of D 2 alone, but the results admit of two other possibilities.Di light may always be present though much fainter than D 2 , or it may only appear under certain conditions.Other resonance phenomena show that the radiation centers in sodium are not entirely independent.One of us 3 showed in 1905 that excitation 1

Physical Review•Jan 1, 1918•37 citations
Abstract In 1874 it was shown by Roscoe and Schuster that channelled absorption spectra can be obtained with the vapours of the alkali elements sodium and potassium, and later on these spectra were investigated in some detail by Liveing and Dewar. It was also shown in 1896 by Weidemann and Schmidt that the vapours of these same metals emitted a radiation possessing characteristics of a fluorescence spectrum when they were traversed by white light. Since 1903 exhaustive studies have been made of both the fluorescence and the channelled absorption spectrum of sodium by R. W. Wood, together with a number of collaborators, Including J. H. Moore and F. E. Hackett. In these investigation it was shown that the channelled absorption spectrum of sodium was made up of a number of series of absorption bands, one set of series being on the red wave-length side of the D lines, and another lying in the visible blue-green region. In addition, series of absorption bands were found by them with approximately regular spacing in the neighbourhood of λ = 3303 A, the second member of the doublet series of this element. As regards the fluorescence spectrum of sodium, they found that, by stimulation of the vapour with approximately monochromatic light, there resulted an emission of light, the spectrum of which consisted of a number of bright but narrow bands of varying intensity, more or less regularly spaced both above and below the mean wave-length of the exciting light. They observed, too, that the slightest change in the wave-length of the exciting light resulted in the disappearance of one set of lines and in the appearance of another of different wave-lengths. In the various florescence spectra obtained by R. W. Wood when stimulating sodium vapour by monochromatic light from different sources, it was noted that there was a remarkable recurrence of the interval, ∆λ = 52·3 A. in the spacing of the fluorescence bands.
Abstract Prof. R. W. Wood has made many interesting observations on the fluorescence of sodium vapour. They are conveniently summarised in his ‘Physical Optics’ (MacMillan, 1911). The fluorescent spectra he has obtained are apparently connected with the banded absorption spectrum of dense sodium vapour. If white light is employed, this banded absorption spectrum is re-emitted completely as a fluorescent emission spectrum. If monochromatic light is used, a portion only of the complete band spectrum is emitted, this portion consisting of a moderate number of lines approximately equally spaced along a normal spectrum, and including a line coincident with the exciting line. These observations on the band spectrum are of great interest and importance, but observations on the line spectrum of sodium, in absorption and in fluorescence, are more within the range of theoretical discussion at the present time.
Abstract A region of continuous absorption lying on the short wave-length side of the limit of the principal series and corresponding to the photo-ionization of the atom is to be expected in the alkali metal vapours. The currents due to photo-ionization have been measured and several attempts have been made to observe the absorption. The main difficulty is in the action of the vapour on the windows of the absorption cell. This has usually been overcome by keeping the ends of the absorption tube cool and checking the diffusion of the vapour from the centre of the tube by means of a foreign gas. This gas produces a large and complicated effect on the absorption (Harrison). In the present experiments it has been found possible to avoid the use of a foreign gas by employing a long absorption tube and a low vapour pressure. Cæsium was used because it gives a sufficient pressure at a moderate temperature and because its series limit lies in the most convenient region of the spectrum.
Abstract In his first papers on the resonance radiation of mercury and sodium Wood describes how the character of the emission changes with increasing pressure of the fluorescent vapour. At low pressure (p = 10-3 mm) the emission comes wholly from a narrow well-defined beam corresponding to the path of the primary light (beam fluorescence). With increasing density of the vapour the beam becomes diffuse until the luminosity fills the whole volume (volume fluorescence) and finally at pressures of about 0·1 mm it withdraws entirely to the spot of entrance of the primary light (surface fluorescence). In all three cases the absorption and emission of light are due to normal atoms; the phenomenon is that of normal or true resonance radiation. For the D-lines of sodium, Lord Rayleigh showed as early as 1919 that, even at pressures at which the true resonance radiation is concentrated on the surface, an emission can in addition be observed within the volume along the path of the primary light, if the D-lines in the spectrum of the exciting source are not too narrow. This new fluorescence beam which can only be excited by the outer parts of the D-lines is partially polarized. Later Jablonsky and Pringsheim found that though the normal resonance radiation observed on the surface is unpolarized under these conditions, the degree of polarization of the new fluorescence beam can be as high as 30% and is practically unaltered by the action of a magnetic field. For the mercury resonance line 2537 A it was Rayleigh who again studied the phenomena at higher pressures but with his main interest concentrated on the duration of the processes and on the appearance of the well-known mercury bands. In his paper, the continuous change of the fluorescence in the vapour volume is studied from room temperature up to 200°C. He used as a source of excitation a “not fully cooled” mercury lamp, giving a somewhat broadened and partially self-reversed line at 2537 A, which produces the effect called by Rayleigh “core­ effect”. The latter is in Rayleigh’s terminology the fluorescence of mercury vapour produced by the more central part of the 2537 A line while the very different fluorescence emission which is excited by a much broadened and self-reversed line is called by him the wing effect. The core effect always shows a line which, with the available dispersion, seems to coincide with the resonance line itself; when the pressure increases, a number of bands appear which have no importance for the present paper. Since in saturated vapour at 100° C the normal resonance radiation has withdrawn to the surface, it is improbable that the core effect is produced by the most central region of the primary line by which the normal resonance radiation at the lowest pressures is excited.
Abstract The first section of this paper is an account of some experiments on the absorption of light in sodium vapour from the series limit at 2412 Å to about 1600 Å (an energy difference of 2·6 eV). The absorption cross-section at the limit is 11·6 ± 1·2 x 10-20 cm2. The cross-section decreases giving a minimum of 1·3 ± 0·6 x 10-20 cm2 at 1900 Å and then increases to 1600 Å. A theoretical calculation by Seaton based on the dipole-length formula gives good agreement with the experiments at the series limit and also correctly predicts the wave-length for the minimum, but it predicts a significantly lower absorption at the minimum. The experiments described in the first section of the paper conclude a series on the absorption of light in the alkali metals. The second section consists of a general discussion of the results of these experiments and of their relation to theoretical calculations. There is good agreement between theory and experiment except in regard to the magnitude of the absorption at the minimum.
Abstract Anomalous dispersion in the region of the red lines of potassium was first observed by Ebert in 1904. The method adopted for Ebert’s experiments was a modified form of the crossed prism method used by Wood in the investigation of the corresponding phenomena in the case of sodium. Potassium was heated in a tube through which two currents of hydrogen passed from each end to a central outlet. The cool hydrogen kept the potassium vapour in a prismatic form, so that light passing along the length of the tube suffered deviation and dispersion by the potassium vapour prism. The author of the present communication has shown that there is no need for the hydrogen streams. If the tube be kept cool on its upper surface the metallic vapour takes of itself a prismatic form or is arranged in layers of decreasing density, and so behaves in a similar way to a prism of homogeneous vapour. The present communication deals with quantitative results from the measurement of dispersions at different wave-lengths, and it appears that the deviation due to potassium vapour is observable over the whole of the visible spectrum and for a considerable distance in the ultra-violet. Strong absorption takes place at the lines of the principal series and for wave-lengths near these series lines we have "anomalous" dispersion. This phenomenon has been observed at seven of the pairs forming the principal series lines for potassium—as the pairs of lines in this series get closer and closer together with diminishing wave-length, the dispersion effects after the first two pairs are only observable outside the lines forming a pair, but there appears a lack of symmetry in the observed dispersion curves corresponding to the different intensities of the lines forming the pair. The dispersion to be observed may then be regarded as that corresponding to the principal series absorption lines; no other absorption region seems to affect the dispersion —at any rate at low densities of vapour.
TPHE purpose of this investigation was to study the resonance spec--*-trum of sodium vapor when the resonance was excited by a single D line.In a paper on " Resonance Radiation of Sodium Vapor "* published by one of us in 1905, it was shown that if a bulb containing pure sodium vapor was illuminated by light from a sodium flame, the vapor emitted a yellow light which spectroscopic analysis showed to be identical with the exciting light, in other words, the two D lines.It was suggested at this time that it would be interesting to see if both D lines appeared when the vapor was illuminated by a single D line.This would determine whether the mechanisms that give rise to the D lines are separate or in some way connected.In 1914 this experiment was tried by Wood and Dunoyer. 2 This experiment was made possible by the discovery of a polarization method of separating close spectral doublets that eliminated the great loss of light involved in a high-power monochromator, but even with this method the resonance light is very faint.The spectrum of resonance excited by D 2 was photographed with exposures varying from 10 to 15 hours.The majority of the plates showed only the D 2 line, but owing to under exposure Di would not have been visible if it was less than one fourth of the intensity of D 2 .Some plates indeed showed both Di and D 2 , but the presence of Di in the exciting light was judged to be the cause of this.Imperfections in the optical system made it impossible to entirely remove Di from the exciting light and as it was sensitive to temperature changes the nature of the transmitted light sometimes changed during an exposure.It was concluded that sodium resonance excited by D 2 consisted of D 2 alone, but the results admit of two other possibilities.Di light may always be present though much fainter than D 2 , or it may only appear under certain conditions.Other resonance phenomena show that the radiation centers in sodium are not entirely independent.One of us 3 showed in 1905 that excitation 1