The continuous hydrogen spectrum

The continuous spectrum of hydrogen in the ultra violet region is intimately connected with the series spectrum given by (35).

This spectrum

) No experiments, which allow to test the preceding results in detail, seem to have been recorded, but it would appear that the above considerations afford an explanation of the general character of the remarkable deviations from a normal Zeeman effect, observed by F Paschen and E. Back (Ann. d. Phys. XXXIX, p. 897 (1912)) in experiments in which the hydrogen lines were excited by passing a powerful condensed discharge through a capillary tube placed at right angles with the direction of the magnetic field. Besides the characteristic want of sharpness of the polarisation of the middle component, exhibited by all the spectrograms published by Paschen and Back, especially one of their photographs (Tafel VIII, Bild 4) seems to suggest the presence of a weak, perpendicularly polarised, diffuse line on each side of the original line and at a distance from it twice that of the outer components of the normal effect. 195 consists of a radiation, the frequencies of which are continuously distributed over a spectral interval extending from the head of the Balmer series in the direction of higher frequencies.1 ) The existence of a continuous spectrum of this type is just what should be expected from a natural generalisation of the principles underlying the quantum theory of series spectra.2 ) Thus the spectrum under consideration may be directly explained by application of relation (1), if we assume that the complete spectrum, emitted by a system consisting of a nucleus and of an electron, originates not only from radiations, emitted during transitions between two states belonging to the multitude of stationary states in which the electron describes a closed orbit, characterised by the condition I = nh, but also from radiations emitted during transitions between two states, one (or both) of which belong to the multitude of states in which the electron possesses sufficient energy to remove to infinite distance from the nucleus. While the electron in the states of the type first mentioned 1 ) This spectrum has been observed as an emission spectrum in spectra of solar protuberances and planetary nebulae (See J. Evershed, Phil. Trans. Roy. Soc. 197 A, p. 399 (1901) and W. H. Wright, Lick Observatory Bulletin, No. 291 (1917)) as well as in direct laboratory experiments on spectra excited by positive rays (See J. Stark, Ann. d. Phys. LII, p. 255 (1917)). Further it has been observed as an absorption spectrum in the spectra of several stars (see W. Huggins, An Atlas of Representative Stellar Spectra, p. 85 (1899) and J. Hartmann, Phys. Zeitschr. XVIII p. 429 (1917)). 2 ) Compare N. Bohr, Phil. Mag. XXVI, p. 17 (1913); and also P. Debye, Phys. Zeitschr. XVIII, p. 428 (1917). 196 may be said to be “bound” by the nucleus to form an atom, it may in the states of the last mentioned type be described as “free”. In order to account for the appearance of the continuous spectrum, it is necessary to assume that the motions in the latter states are not restricted by extra-mechanical conditions of the type holding for the former states, but that all motions, which are consistent with the application of ordinary mechanics, will represent physically possible states. This assumption would also seem to present itself naturally from the point of view on the principles of the quantum theory, taken in the present paper.1 ) Thus it will in the first place be observed that any attempt to discriminate between the different states of the type in question, by means of considerations of the mechanical stability of stationary states for slow transformations of the external conditions, would fail on account of the essentially non-periodic character of the motion, which is irreconcilable with the idea of invariance of extra-mechanical conditions for such transformations.

Next, with reference to the formal analogy between the quantum theory and the ordinary theory of radiation, it will be seen that the fact, that the motion of a free electron in its hyper1) A view contrary to this has been taken by Epstein, who in a recent paper (Ann. d. Phys. L, p. 815 (1916)) has made an attempt to obtain an explanation of certain observations on the photoelectric effect of hydrogen occluded in metals, by applying conditions of the same type as (22) to states of the hydrogen atom in which the electron describes a hyperbolic orbit, and has tried in a similar way to develop a theory of the characteristic β-ray spectra of radioactive substances.

bolic orbit cannot be resolved in a sum of harmonic vibrations of discontinuously varying frequencies but can only be represented by a Fourier integral extended over a continuous range of frequencies, suggests beforehand that the free electron may pass, under emission or absorption of radiation, to any one among a continuous multitude of other states corresponding to a continuous multitude of values for the energy of the system. From the preceding considerations we may infer, by application of (1), that the complete spectrum emitted by the hydrogen atom will, besides the series spectrum and the continuous ultra-violet spectrum mentioned above, which corresponds to transitions from a state in which the electron is free to a stationary state characterised by n = 2 in (41), contain a set of continuous spectra, corresponding to transitions from free states to other stationary states, and each extending in the direction of larger frequencies from one of the values of the frequency, given by (35) if we put n 0 = ∞. Moreover, we may expect the presence of a weak continuous spectrum, extending as a continuous back ground over the whole region of frequencies, which will correspond to transitions between two different states in both of which the electron is free. The relative intensities of these different continuous spectra, and the laws according to which the intensity is distributed within each of them, may be expected to vary to a large extent according to the different conditions under which the radiation is excited.

Thus, while the continuous spectrum of hydrogen, when observed as emission spectrum in stars, shows a abrupt beginning at the head of the Balmer series, the continuous spectrum, observed by Stark in his experiments referred to above, was not sharply limited but showed a pronounced maximum in the spectral region which corresponds to transitions between two states, in the first of which the velocity of the free electron relative to the nucleus, before the “collision” with the latter, was of the same order of magnitude as the velocity of the positive rays by means of which the spectrum was excited.

Besides the series spectrum and the connected continuous spectrum just considered, there exists, as well known, another hydrogen spectrum, the so called many-line spectrum, which on account of its complex structure and its resemblance with the band spectra, emitted by other elements and combinations of elements, is generally ascribed to the hydrogen molecule and not to the atom.

This assumption would also seem to present itself directly from the point of view of the quantum theory, according to which the simple structure of the series spectrum is directly connected with the simple periodic character of the motion of the particles in the atom, while a spectrum of a complexity of the order exhibited by the many-line spectrum must be assumed to originate from a system the motion of which does not show such simple periodicity properties. The problem of the constitution of the hydrogen molecule, to be expected on the quantum theory, and the possible motions of the particles of this system will be treated in Part IV.

In this connection we shall also consider the problem of dispersion of light in hydrogen gas and the problem of the voltage necessary to produce the lines of the series spectrum of hydrogen by an electric discharge in this gas.