scholarly journals The ultra-violet spectrum of magnesium hydride. 1.—The band at λ 2430

The system of bands in the visible region of the emission spectrum of magnesium hydride is now well known. The bands with heads at λλ 5622, 5211, 4845 were first measured by Prof. A. Fowler, who arranged many of the strongest lines in empirical series for identification with absorption lines in the spectra of sun-spots. Later, Heurlinger rearranged these series in the now familiar form of P, Q and R branches, and considered them, with the OH group, as typical of doublet systems in his classification of the fine structure of bands. More recently, W. W. Watson and P. Rudnick have remeasured these bands, using the second order of a 21-foot concave grating, and have carried out a further investigation of the fine structure in the light of the present theory of band spectra. Their detection of an isotope effect of the right order of magnitude, considered with the general structure of the system, and the experimental work on the production of the spectrum, seems conclusive in assigning these bands to the diatomic molecule MgH. The ultra-violet spectrum of magnesium hydride is not so well known. The band at λ 2430 and the series of double lines in the region λ 2940 to λ 3100, which were recorded by Prof. Fowler in 1909 as accompanying the group of bands in the visible region, appear to have undergone no further investigation. In view of the important part played by hydride band spectra in the correlation of molecular and atomic electronic energy levels, it was thought that a study of these features might prove of interest in yielding further information on the energy states of the MgH molecule. The present paper deals with observations on the band at λ 2430; details of an investigation of the other features of the ultra-violet spectrum will be given in a later communication.

During the course of investigation of the bands at λλ 5622, 5211 and 4845, emitted by the magnesium arc in hydrogen at low pressures, Prof. A. Fowler observed that they were always accompanied by a further band at λ 2430 and by series of double lines in the region λ 2940 to λ 3100. These features of this spectrum seemed to merit further study in view of the important part played by the spectra of other molecules with 13 electrons (CN, BO, BeF, CO + , N 2 + ) in the classification of molecular energy levels. Further, MgH is one of the interesting series of hydrides (BeH, MgH, CaH, ZnH, CdH, HgH) which show a pair of excited P states, with doublet separation increasing with molecular weight, closely resembling the lowest 2 P state of the preceding monovalent atoms (Li, Na, K, Cu, Ag, Au). An account of an analysis of the band at λ 2430 was given in a previous paper; the present paper deals with the series of double lines. For convenience the system in the visible region is referred to as the α-system, the one represented by the band at λ 2430 as the β-system, and that about to be described as the γ-system.


Measurements of the refractive indices, the low-(radio)-frequency dielectric constant, the ultra-violet absorption spectra and the photoconductivity of silver azide have been made. The absorption spectra have been measured at room temperature, at —80 and at —175° C. The photoconductivity has been measured as a function of time of illumination, electric field strength, wavelength, intensity of illumination at various wavelengths, and temperature. The measurements suggest that the absorption of light in the crystal produces excitons and that the photoconductivity is a direct result of the dissociation of these excitons into free electrons and positive holes. The electronic energy levels of the crystal, as determined from these measurements, have been used to calculate the activation energies for the slow photochemical and thermal decomposition of silver azide.


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