Popular Science Monthly/Volume 8/February 1876/The Nature of Fluorescence
By Dr. EUGENE LOMMEL,
PROFESSOR OF PHYSICS IN THE UNIVERSITY OF ERLANGEN.
THE question now arises. What becomes of the rays that have undergone absorption? Are they in fact, as they appear to be, annihilated? A series of phenomena now to be considered will give ns an answer to these questions.
If water containing a little esculine, a substance contained in the bark of the horse-chestnut in solution, be placed in a flask, and the Fig. 1.—Illumination of Flourescence. rays of the sun or of the electric lamp, concentrated by a lens situated at about its focal distance from the vesel (Fig. 1), be directed upon it, the cone of light thrown by the lens into the interior of the fluid will be seen to shine with a lovely sky-blue tint. The particles of the solution of esculine in the path of the beam become spontaneously luminous, and emit a soft blue light in all directions. The cone of light appears brightest at the point where it enters into the fluid through the glass, and quickly diminishes in brilliancy as it penetrates more deeply.
There are great numbers of fluid and solid bodies which become similarly self-luminous under the influence of light. This peculiarity was first observed in a kind of spar occurring at Alston Moor, in England, which, itself of a clear green color, appears by transmitted solar light of a very beautiful indigo-violet color. From its occurrence in calcium fluoride the phenomenon has been named florescence.
In order to understand more precisely the circumstances under which fluorescence occurs, the solution of esculine must again be referred to. The light, before it reaches the lens, must be allowed to pass through just such another solution of esculine contained in a glass cell with parallel walls. The cone of light proceeding from the lens, as long as it passes through the air, does not appear to have undergone any material change, it is just as bright and just as white as before. In the interior of the fluid, however, it no longer presents a blue shimmer, but becomes scarcely perceptible.
Thus it is seen that light which has traversed a solution of esculine is no longer capable of exciting fluorescence in another solution of esculine. Those rays consequently which possess this property must be arrested by the first solution of esculine. Similar results are obtained in the case of every other fluorescent substance.
The general proposition can therefore be laid down, that a body capable of exhibiting fluorescence fluoresces by virtue of those rays which it absorbs.
In order to determine what rays in particular cause the fluorescence of esculine, the spectrum must be projected in the usual way; but, instead of its being received upon a paper screen, it must be allowed to fall upon the wall of a glass cell containing a solution of esculine, that is to say, upon the solution itself, and it must then he observed in what parts of the spectrum the blue shimmer appears. The red and all the other colors consecutively down to indigo appear to be absolutely without effect. The bluish shimmer first commences in the neighborhood of the line G (Fig. 2), and covers not only the violet part of the spectrum, but stretches far beyond the group of lines H to a distance which is about equal to the length of the spectrum visible under ordinary circumstances.
From this the conclusion must be drawn that there are rays which are still more refrangible than the violet, but which in the ordinary mode of projecting the spectrum are invisible; these are termed the ultra-violet rays. They become apparent in the esculine solution because they are capable of exciting the bluish fluorescent shimmer in it. If sunlight have been used in the above experiments, the well-known Fraunhofer's lines appear upon the bluish ground of the fluorescing spectrum, not only from G to H, but the ultra-violet part also appears filled with numerous lines, the most conspicuous of which are indicated by the several letters L to S (Fig. 2). That these lines, like the ordinary Fraunhofer's lines, belong properly to solar light, and do not depend upon any action of the fluorescing substance, is evident from the circumstance that with the electric light they are no more apparent in the ultra-violet than in the other colors, and further, because the same lines are seen in the solar spectrum, whatever may be the fluorescing substance under examination.
Quartz has the power of transmitting the ultra-violet rays far more completely than glass. If, therefore, the glass lens and prism hitherto used for projecting the spectrum be replaced by a quartz lens and prism, the ultra-violet part of the spectrum is rendered much brighter and is extended still farther than before.
The ultra-violet rays of the spectrum can, moreover, be seen, without the intervention of any fluorescing substance, through a glass, or, still better, through a quartz prism, if the bright part of the spectrum between B and H (Fig. 2) be carefully shut off. With feeble illumination its color appears indigo-blue, but with light of greater intensity it is of a bluish-gray tint (lavender). The ultra-violet rays thus ordinarily escape observation, because they produce a much feebler impression on the human eye than the less refrangible rays between B and H.
An explanation is thus afforded why the solution of esculine, apart from its absorption, is colorless when seen by transmitted light; for, since it absorbs only the feebly luminous violet and the entirely imperceptible ultra-violet rays, the mixed light that has passed through it still appears white, and is not rendered materially fainter.
If the solar spectrum be thrown in the above-mentioned manner upon the fluid, its fluorescing part everywhere exhibits the same bluish shimmer; and spectroscopic examination shows that this bluish light has always the same composition, whether it is excited by the G rays, or by the H rays, or by the ultra-violet rays, and that it is formed of a mixture of red, orange, yellow, green, and blue. It is thus seen that the different kinds of homogeneous light, as far as they are generally effective, produce compound fluorescent light of identical composition, the constituents of which, nevertheless, are collectively less refrangible than, or are at most equally refrangible with, the exciting rays.
Among other fluorescing bodies may be mentioned the solution of quinine, which is as clear as water, and has a bright-blue fluorescence; the slightly yellow petroleum, with blue fluorescence; the yellow solution of turmeric, with green; and the bright-yellow glass containing uranium, which fluoresces with beautiful bright-green fluorescence. It admits of easy demonstration that in these bodies also it is the more refrangible rays that call forth fluorescence. For, if we illuminate them with light which has passed through a red glass, no trace of fluorescence is visible. But, if the red be exchanged for a blue glass, the fluorescence becomes as strongly marked as Avith the direct solar light. A remarkable phenomenon is presented in the splendid bright-green light which is emitted by uranium glass under the action of blue illumination.
The highly-refrangible rays which possess in so high a degree the power of exciting fluorescence are contained in large proportion in the light emitted by a Geissler's tube filled with rarefied nitrogen. In order to expose fluorescing fluids to the influence of this light, the arrangement represented in Fig. 3 may be employed with advantage, A narrow tube is surrounded by a wider glass tube, into which the fluid is introduced by a side opening which can be closed if required. Another form of Geissler's tube is represented in Fig. 4, which contains
in its interior a number of hollow spheres composed of uranium glass. Where a beam of reddish violet nitrogen light traverses the tube, the uranium glass balls shine with a beautiful bright-green fluorescent light.
The electric light passing between carbon-points is rich in rays of high refrangibility, indeed the ultra-violet end of its spectrum reaches even farther than that of the solar spectrum. In the light of the magnesium-lamp the ultra-violet rays are also abundant, and both sources of light are therefore particularly well adapted to produce fluorescence, while gas and candle light are nearly inoperative on account of the small amount of the more refrangible rays they contain.
It would nevertheless be incorrect to infer from the above facts that the more refrangible rays are exclusively capable of exciting fluorescence. A red fluid which is an alcoholic solution of naphthaline red, and which in ordinary daylight fluoresces with orange-yellow tints of unusual brilliancy, will serve to demonstrate that even the less refrangible rays are capable of producing this effect. In fact, if the spectrum be projected upon the glass cell containing the fluid (Fig. 5), the yellow fluorescent light will be seen to commence at a point intermediate to C and D and therefore still in the red, and to
Fig. 5.—Absorption and Fluorescing Spectrum of Naphthaline Red.
extend over the whole remaining spectrum as far as the ultra-violet. The strongest fluorescence by far is shown behind the line D in the greenish-yellow rays. It then again diminishes, and becomes a second time more marked between E and b; thence onward the fluorescence becomes fainter, then increases again in the violet, and gradually vanishes in the ultra-violet. In naphthaline red, therefore, there are rays of low refrangibility, namely, the green-yellow rays behind D, by which its fluorescence is most powerfully excited.
The fluorescence spectrum received upon the fluid shows, as we have already mentioned, three regions of stronger fluorescence, and the absorption spectrum of naphthaline, which, by placing a small cell filled with the solution in front of the slit, may be obtained upon a paper screen, gives a key to the cause of this phenomenon. In this spectrum Fig. 5 (1), a completely black band is visible in the green-yellow behind D, a dark band between E and b, while the violet end appears shaded. On employing a very strong solution of the naphthaline coloring material, the whole spectrum vanishes with the exception of the red end, which remains apparent to a point behind C. If now the absorption spectrum be compared with that thrown upon the fluid, the intimate relation between absorption and fluorescence that has already been pointed out in the esculine solution is corroborated in the minutest particulars. For every dark hand in the absorption spectrum corresponds to a bright band in the fluorescing spectrum. Every ray absorbed by the fluid occasions fluorescence, and the fluorescent light produced is the brighter, the more completely the ray is absorbed.
A second example of the excitation of fluorescence by rays of small refrangibility is exhibited by a solution of chlorophyll. The spectrum projected upon this green fluid fluoresces of a dark-red color, from B to a point within the ultra-violet, exhibiting at the same time bright bands which correspond with the dark bands in the absorption spectrum. Between B and C, where the greatest amount of absorption occurs, the fluorescence is also the most marked. But it is the middle red rays which here act so powerfully as excitants. It is remarkable that the red fluorescent light which the chlorophyll solution emits likewise lies, in regard to its refrangibility, between B and C. Chlorophyll solution affords a proof that all rays of the spectrum, with the exception of the extreme red in front of B, are capable of calling forth fluorescence. Their capacity for doing so depends simply on the power of absorption of the fluorescing substance. The most refrangible violet and ultra-violet rays are, however, characterized by the circumstance that they are capable of exciting all known fluorescing bodies.
Fluorescent light is only perceived so long as the fluorescent substance is illuminated by the exciting rays. As soon as the light falling on it is obstructed, the colored shimmer vanishes. It is only in the case of some fluorescing solid substances, as, for example, fluorspar and uranium glass, that, with the aid of appropriate apparatus (Becquerel's phosphoriscope), a very short continuance of the fluorescence may be observed to take place in the dark.
There are, however, a number of bodies which, after being excited to self-luminosity by a brilliant light, continue to shine for a certain time in the dark. A series of pulverulent white substances, namely, the sulphur compounds of calcium, strontium, and barium (which should be kept in hermetically-sealed glass tubes), do not exhibit the faintest light in a dark room. Moreover, if they be covered with a yellow glass and illuminated with the light of a magnesium-lamp, they remain as dark as before. But if the yellow be exchanged for the blue glass, and the magnesium-light be allowed to play upon them for a few seconds only, they emit in the dark a soft light, each powder having its own proper tint of color. This power of shining in the dark after having been exposed to the light is called phosphorescence. The property is possessed in a high degree not only by the above-named artificially-prepared substances, but by various minerals, as the diamond, fluor-spar, and a variety of fluor-spar called chlorophane.