Overlapping energy bands and the theory of collective electron ferromagnetism

1953 ◽  
Vol 49 (1) ◽  
pp. 115-129 ◽  
Author(s):  
A. B. Lidiard

ABSTRACTThe theory of collective electron ferromagnetism given by Stoner applies to a system of electrons in a single energy band; for iron, cobalt and nickel this is identified with the band of states derived from atomic 3d functions. To bring in the generally assumed overlapping of the 3d band by the wide 4s band in these metals, the theory has been extended to take account of the transfer of electrons from 3d to 4s states with change of temperature. A previous calculation of this transfer effect must be regarded as inadequate, for the part played by the exchange energy in determining the distribution of electrons between the two sets of states was omitted. The general equations are derived in § 2 and used as a basis for discussion of the properties of nickel-copper alloys at absolute zero in § 3. In §§4 and 5 numerical results are presented which show the effect of the overlapping 4s band on the magnetic properties of a system such as nickel both above and below its Curie point. Comparison with the measured paramagnetic susceptibility of pure nickel above the Curie point strongly suggests that for this metal the overlapping 4s band has only a minor influence, although in principle the effect could be very large (cf. Fig. 4). This result is not unambiguous, however, because values thus inferred for the two unknown parameters lead to inaccurate predictions below the Curie point. First, the predicted values for the spontaneous magnetization are too small. Secondly, the theory demands that the nickel-copper alloys should only be ferromagnetic below a copper content of about 20 %, whereas experimentally the limit is known to be about 60 %. In conclusion, it is suggested that the implicit assumption of Stoner's theory that the exchange integrals between all pairs of 3d states are equal to one another is a more serious restriction on the theory than the consideration of only a single energy band.

The collective electron treatment of ferromagnetism (Stoner 1938 a , 1939) is applied to the magnetic and thermal properties of nickel and nickel-copper alloys. In § 1 a brief description is given of the theoretical background, together with the necessary extensions of the basic treatment, in particular so as to cover the effects of the overlap of the electronic d and s energy bands. With simplifying assumptions regarding the effect of alloying on the electronic structure, and using a limited range of observational data, estimates are obtained of the variation of the specifying parameters, band width and interchange interaction, for nickel-copper alloys, over a wide range of composition (§ 2). A discussion is given in § 3 of the dependence of the electron distribution on temperature. Calculations are carried out of the variation of the number of holes in the d band, due to the temperature redistribution of electrons between the bands (transfer effect). Other temperature effects, such as the variation of the specifying parameters due to thermal expansion, are briefly discussed, though they are not included in the main treatment (§§ 1 and 4). The treatment is applied to the temperature variation of susceptibility above the Curie point (§4). For nickel-rich alloys satisfactory agreement is obtained with experimental results (figures 10, 11 and 12). For copper-rich alloys the observed high-temperature increase of susceptibility is well explained (figure 13), but no interpretation can be given of the observed low-temperature variation. It is suggested that this may be due to inhomogeneities in composition. A discussion is given in § 5 of the bearing of the treatment on the electronic heat at high temperatures. Comparison is made with the relevant experimental results for nickel above the Curie point. Application is also made to the low-temperature electronic heat of nickel-copper alloys (§5). The general character of the variation of the electronic heat with composition is covered satisfactorily in the nickel-rich regions, but in the copper-rich regions discrepancies occur, similar to those for the low-temperature susceptibility (§4). In §6 a brief account is given of the results of a preliminary analysis of the magnetic properties of nickel alloys other than those with copper.


The collective electron theory of ferromagnetism is extended to include in the expression for the energy associated with the magnetization a term in the fourth power of the magnetization. A second adjustable parameter, similar to the kθ'/ϵ 0 of the Stoner treatment, is thus introduced. Detailed comparison with experiment of a number of properties of nickel, nickel-cobalt and nickel-copper alloys, is carried out. A high degree of co-ordination of the properties of nickel is obtained by a suitable choice of the two parameters, which are thereby determined within fairly close limits. The temperature variation of electronic specific heat and spontaneous magnetization of nickel is quantitatively covered, as is the magnetocaloric temperature change accompanying changes in external field. The spontaneous magnetization, temperature curves of cubic cobalt and four nickel-copper alloys are similarly covered, and a simple interpretation can be given of the adherence to the law of corresponding states of nickel-cobalt alloys and the deviation therefrom of the nickel-copper alloys. The model accounts qualitatively for the field-magnetization isothermals and for the variation of the magnetocaloric temperature change with magnetization. A detailed examination shows that the differences between theory and observation, where they exist, are due to effects not covered by the collective electron theory. The main discrepancies can be accounted for on the assumption that a small fraction of the volume of the material is made up of groups of atoms of varying size with a Langevin distribution of their magnetic axes. These groups may be called small domains. The problem is complicated by the fact that the field values computed theoretically are critically dependent on the parameters, of which a sufficiently close estimate cannot be made. However, for particular values of both kθ'/ϵ 0 and A a good fit with experiment over a wide temperature range is obtained when it is assumed that the domains are of sizes varying from 10 3 atoms upwards, the largest proportion of domains being of 10 4 to 10 5 atoms, and the volume occupied by such domains probably being much less than 10% of the total volume of material. It is shown that the hitherto unexplained large temperature variation, derived from the experimental results, in the value of —1/ σ (∂ E /∂ σ ) T corresponding to the Weiss molecular field coefficient, is an almost direct consequence of the basic physical premises of the collective electron treatment.


The essential contribution of Heisenberg to the theory of ferromagnetism was in showing that those effects which had been correlated by means of the formal molecular field hypothesis of Weiss could be interpreted as arising from interchange interaction between electrons in atoms, of the same type as that involved in the formation of homopolar molecules. The Heisenberg method of approach has, however, proved in many ways less convenient in the detailed treatment of ferromagnetism than the method initiated by Bloch for the theory of metallic properties generally, in which possible energy states are derived for electrons treated as waves travelling through the whole crystal. The first approximation in this collective electron treatment is that of free electrons, for which the energy is purely kinetic, the number of states per unit energy range then being proportional to the square root of the energy. The effect of the periodic field of the lattice is to modify the distribution of states, giving rise to a series of energy bands, separate or overlapping. Elaborate calculation is necessary to determine the form of these bands with any precision, though in general near the bottom of a band the energy density of states depends on the energy in the same way as for free electrons, but with a different pro­portionality factor; this holds also near the top of a band, the energy being measured downwards from that limit. The salient characteristics of metals depend on the electrons in unfilled bands. In particular, in the ferro­magnetic metals, iron, cobalt and nickel, the ferromagnetism may be attributed to the electrons in the partially filled band corresponding to the d electron states in the free atoms. The exchange interaction is such that, at low temperatures, instead of the electrons occupying the lowest states in balanced pairs, there is an excess of electrons with spins pointing in one direction, giving rise to a spontaneous magnetization. The decrease of energy due to the exchange effect with increase in the number of excess parallel spins is accompanied by an increase due to the electrons moving to states of higher energy in the band. The equilibrium magnetization depends on the number of electrons, the form of the band, the magnitude of the exchange interaction, and the temperature, and must be calculated on the basis of Fermi-Dirac statistics. The primary purpose in this paper is the determination of the form of the magnetization temperature curves for bands of the standard type and for a range of values of the exchange interaction energy. Before discussing the particular problem more fully, the relation between the present and some of the previous work will be briefly indicated. The advantages of a collective electron treatment for ferromagnetism were pointed out some years ago in a paper (Stoner 1933) in which it was shown that such a treatment enabled an immediate interpretation to be given to the non-integral values of the atomic moments of the ferromagnetic metals, and of the variation of the moment with small additions of non­ferromagnetic metals in alloys. Little was then known about the form of the electronic energy bands in transition metals, and the treatment was necessarily qualitative. Considerably greater precision in formulation became possible on the basis of a suggestion by Mott (1935), having a general justification, on the form of the energy bands in the ferromagnetic metals. In nickel, in particular, it was suggested that a narrow d band was overlapped by a much wider s band, and that the top of the Fermi distri­bution came at a point corresponding to 0·6 electron/atom in the s band, with a deficit of the same number in the d band; this number corresponding to the observed saturation moment of nickel at low temperatures. (It may be noted that “holes” in bands are to a large extent magnetically equi­valent to the same number of electrons in otherwise empty bands, as is more fully discussed elsewhere (Stoner 1936 a ).) This general idea of Mott has been developed successfully in a number of directions (cf. Mott and Jones 1936). A first step in the quantitative treatment of the effect of temperature on the magnetic properties of metals was the determination of the temperature dependence of free electron susceptibility (Stoner 1935, 1936 b ); the results obtained are applicable not only to free electrons but also to electrons in unfilled bands with the same type of energy distri­bution of states. Series expressions were derived appropriate to high and low temperatures, and values for the intermediate temperature range were found by graphical interpolation. In a subsequent discussion on spin paramagnetism in metals (Stoner 1936 a ) a simple method of taking into account the effect of interchange interaction was described, the method being applicable to the determination of the temperature variation of the susceptibility of a ferromagnetic above the Curie point. Shortly after­ wards the treatment was extended to deal with the spontaneous magnetization below the Curie point and the general character of the modifications resulting from the use of Fermi-Dirac, in place of classical, statistics, was determined. It was found, however, that the method previously used, involving series calculations for high and low temperatures, and graphical interpolation, was inadequate to give numerical results of satisfactory precision, the lack of precision being most marked for the temperature range which was often of greatest interest as including the Curie point region. For precise numerical results, an accurate evaluation of a series of the basic Fermi-Dirac functions was indispensable. An extensive table of Fermi-Dirac functions is now available (McDougall and Stoner 1938) and this provides the necessary starting point for much of the computational work involved in the present paper.


The spontaneous magnetization (σ 0 , T ) of a ferromagnetic may be deduced exclusively from the determination of magnetic isothermals, or in conjunction with magnetocaloric measurements. Values of σ 0, T of a nickel + copper alloy containing 30·75 at. % of copper have been obtained near its Curie temperature using both of these techniques and are shown to be in good agreement. Measurements of spontaneous magnetization and Curie temperature ( θ f ) of nickel + copper alloys containing up to 54·11 at. % of copper using the purely magnetic techniques are described. These measurements were performed over a temperature range from θ f down to 80 °K in all cases, and to 23 °K in the cases of alloys containing over 30 at. % of copper. The magnetic moments per atom ( p B ) of the alloys, which are deduced from the measurements, vary linearly over a wide range of composition, extrapolating to p B = 0 at 53 at. % of copper. This value is in good agreement with that obtained by Meyer & Wolff (1958), and contrary to that based on the familiar measurements of Alder (1916). The reduced magnetization-temperature curves of some of the alloys are given and these show a continuous marked decrease in fullness with increasing copper content.


Author(s):  
Michael Joshua Landau

Acoustical properties of speech have been shown to be related to mental states such as remission and depression. The objective of this project was to relate the energy in frequency bands with the severity of the mental state using the Beck Depression Inventory (BDI). Recorded speech was obtained from male and female subjects with mental states of remission, depression, and suicidal risk. These subjects had recorded automated and spontaneous speech samples. Multiple regression analysis was used to relate the independent energy band ratio variables with the dependent BDI scores, and thus allow the determination of equitable BDI scores for future patients. For the male group, the square of the 3rd energy band and the cross-product of the 2nd and 3rd energy band were prominent in both the reading and interviewed groups. Therefore the equation with the 2nd lowest Akaike Information Criterion (AIC) score was chosen for the reading male group, and the 1st lowest AIC score was chosen for the interviewed male group. For the female group, the square and cross-product of the 1st and 2nd energy bands were prominent in both the reading and interviewed groups. Therefore the 2nd lowest AIC score was chosen for the reading female group, and the 1st lowest AIC score was chosen for the interviewed female group. The clinician could thus determine the patient’s mood or state of mind by comparing the estimated BDI score with the ranges of total BDI scores: remitted 0 – 20, depressed 15 – 38, suicidal 38 – 46. Keywords: speech, mental states, power spectra, multiple regression, information theoretic criterion


1984 ◽  
Vol 24 (4) ◽  
pp. 305-323 ◽  
Author(s):  
R.D.K. Misra ◽  
G.T. Burstein

1979 ◽  
Vol 92 (2) ◽  
pp. 379-387 ◽  
Author(s):  
P. Plenkiewicz ◽  
B. Dowgiałło-Plenkiewicz

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