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- Strong magnetoelastic effect in
CeCo1xFexSi as Néel order is suppressed
V. F. Correa et al
536.76 + 538.2
MAGNETIC FIRST ORDER PHASE TRANSITIONS
N. P. GRAZHDANKINA
727
728 N. P . GRAZHDANKINA
w h i c h l e a d s t o a d e c r e a s e o f t h e f r e e e n e r g y w i t h i n -
2
c r e a s i n g cr, s i n c e t h e c o e f f i c i e n t o f cr i s n e g a t i v e . W i t h
f u r t h e r i n c r e a s e o f a , t h e c o n t r i b u t i o n o f t h e t e r m s
4 8
c o n t a i n i n g a a n d a i n c r e a s e s , a n d t h i s l e a d s t o a n i n -
v — v B
(2.3) T h e c h a r a c t e r o f t h e p h a s e t r a n s i t i o n i s d e t e r m i n e d b y
t a i n i n g cr 4 l e a d s t o a m i n i m u m o f t h e f r e e e n e r g y a t
a s* 0 , a n d t h i s , a s a l r e a d y n o t e d , c a u s e s a first-order
Relation (2.4) contains the parameter TJ, the absolute transition. T h e f o r e g o i n g i s i l l u s t r a t e d b y p l o t s of
values of which determine the character of the magnetic ( G o - G a ) / G o a g a i n s t a, c a l c u l a t e d f o r TJ = 1 . 2 a t P = 0
phase transition in each concrete case. r\ > 1 for first- a n d d i f f e r e n t v a l u e s of T / T o ( F i g . 2 ) .
order transitions and TJ < 1 for second-order transitions. A more general criterion determining the character
This can be verified by examining the cr = f (T/To) depen- of t h e p h a s e t r a n s i t i o n u n d e r c o n d i t i o n s of c o m p r e s s i o n
dence expressed by Eq. (2.4). Figure 1 shows the tem- of m a t t e r w a s d e r i v e d o n t h e b a s i s o f ( 2 . 6 ) a n d (2.7),
perature dependence of the magnetization for different namely
values of the parameter TJ. For the case r\ = 0 and P = 0,
we have the usual functional dependence of a on T/T o , Pxf, > 1 - (2.8)
determined by the Brillouin function. When r\ < 1, as The r e l a t i o n (2.8) i n d i c a t e s that an e x t e r n a l p r e s s u r e
seen from the curves of Fig. 1, the transition is of sec- c a n c h a n g e t h e c h a r a c t e r of t h e m a g n e t i c transformation.
W h e r e a s , for e x a m p l e , at a t m o s p h e r i c p r e s s u r e (for t h e
c a s e p > 0) t h e m a g n e t i c t r a n s f o r m a t i o n w a s a f i r s t -
o r d e r t r a n s i t i o n , at high p r e s s u r e s the t r a n s f o r m a t i o n
can become a second-order transition.
In c o n c l u d i n g t h i s s e c t i o n , l e t u s d w e l l o n t h e q u a l i t a -
t i v e a n a l o g y b e t w e e n t h e d e t e r m i n a t i o n o f t h e t y p e of t h e
m a g n e t i c p h a s e t r a n s i t i o n b y t h e t h e o r y of B e a n a n d
o n d o r d e r , w h e r e a s w h e n TJ > 1 t h e t r a n s i t i o n a t t h e
C u r i e p o i n t i s of f i r s t o r d e r . The dashed CT(T/T0) curve
for rj = 4 s h o w s t h e n o n - e q u i l i b r i u m s t a t e s of t h e m a g -
n e t i c o r d e r i n g , c o r r e s p o n d i n g t o t h e m a x i m u m of t h e
f r e e e n e r g y ( s t a t e s w i t h s u c h v a l u e s of a c a n n o t b e r e a l -
ized). T h e a n a l y s i s of t h e d e p e n d e n c e of t h e f r e e energy
on the magnetization i s b a s e d on the e x p r e s s i o n
-5 •
IT . „ 2HoBo
NkT0
F I G . 2 . P l o t s o f t h e free e n e r g y a g a i n s t a as c a l c u l a t e d b y R o d b e l l
2
a n d B e a n [ ] for t h e c a s e j = 1/2 a n d 7? = 1.2. T h e n u m b e r s at t h e c u r v e s
( 2 . 5 ) c o r r e s p o n d t o t h e ratio T/T o
.
730 N. P . GRAZHDANKINA
Rodbell and the general thermodynamic theory of phase starting from relation (2.4). The second criterion is the
transitions of Landau and Iifshitz 153 . This analogy was sign of the coefficient b, which is determined from mag-
emphasized by Banerjee [14] . As is well known, the netic measurements only, in accordance with Eq. (2.10).
theory of Landau and Iifshitz is based on general The available experimental data, which will be discussed
thermodynamic relations with allowance for the symme- later, offer evidence that the relation (2.4) is satisfac-
try properties of the crystal. It is assumed here that torily valid.
the thermodynamic potential *(T, P, | ) can be expanded
in a series about the transformation point, where the
ordering parameter | is small*. Vonsovskii [6: and 3) Investigation of Magnetic Transformations in Man-
Ginzburg [7] used this theory to study phase transitions ganese Arsenide and Comparison of the Experimental
at the Curie points of ferromagnets, using the magne- Data with the Theory
tization of the material (f = cr) as the ordering param- The theory developed by Bean and Rodbell t2] was used
eter. When account is taken of the energy of the external by them, and also by Rodbell and de Blois cl5] to explain
magnetic field, the expansion of the thermodynamic po- the magnetic transformations in manganese arsenide.
tential is of the form In spite of the many investigations of the magnetic trans-
formations in MnAs, the nature of these transformations
— <sH, (2.9) is not yet fully clear. The experimental investigations
where a and b are coefficients that depend on P and T. of Guillaud[16] and Serres t l 7 ] have shown that at tem-
At equilibrium, near the Curie point, 8*/3a = 0; on this peratures 313 and 399°K the magnetic properties of
basis, Eq. (2.9) can be rewritten in the form MnAs experience a change. At low temperatures, MnAs
has ferromagnetic properties; near 313°K a sharp drop
aa + ba^H. (2.10) of the magnetization takes place, accompanied by a
A thermodynamic analysis of the properties of the co- change of the volume and by release of the latent heat of
efficients a and b indicates that at the Curie point a = 0 the transformation. In the temperature interval from
and b should always be positive for second-order phase ©i = 313 to ©2 = 399°K, an increase of the susceptibility
transitions. Perfectly analogous conclusions can be is observed with increasing temperature, and only above
drawn also on the basis of the theory of Bean and Rod- 399°K does MnAs become paramagnetic and its suscep-
bell. Indeed, Eq. (2.5), obtained in the theory of Bean tibility obeys the Curie-Weiss law. These magnetic
and Rodbell, can be written in the form of (2.11), if the transformations are accompanied by changes of the
terms that do not depend on a are denoted by Ao: crystal structure. In the ferromagnetic (T < ®i) and
paramagnetic (T > ®2) states, MnAs has a lattice with
-g^-^-Ao + Atf + B^-Ho. (2.11) hexagonal symmetry D4jj. The magnetic transformation
©i causes an orthorhombic distortion of the crystal lat-
This equation corresponds to Eq. (2.9), and the condi- tice, which vanishes at the temperature ®2 :18] . In
tion A = 0, B > 0, which defines a second-order phase Guillaud's opinion, change of the magnetic properties of
transition in the theory of Bean and Rodbell, is perfectly MnAs can be explained by assuming that at ©i = 313°K
analogous to the condition for second-order phase tran- a transition takes place from the ferromagnetic into the
sitions in the theory of Landau and Iifshitz (a = 0, b >0). antiferromagnetic state, and at ©2 = 399° K the inverse
C14]
On this basis, Banerjee proposes that the theory of transition takes place. This assumption was confirmed
Landau and Iifshitz can be generalized also to include by Meyer and Taglang ci9] , who investigated the magneto-
the case of first-order phase transitions, the condition caloric effect of MnAs and observed a reversal of the
for which, in analogy with the theory of Bean and Rod- sign of the effect at 310 and 390° K. From thermody-
bell, should be taken to be a = 0 and b < 0. For an ex- namic considerations, it could be assumed that the ob-
perimental determination of the character of a magnetic served increase of the temperature under adiabatic de-
phase transition, Banerjee proposes to use the method magnetization of the sample is connected with antiferro-
t4]
of "thermodynamic coefficients," developed by Belov magnetic ordering of the spin magnetic moments of
and widely used at present for a precision determina- MnAs in the indicated temperature interval. However,
tion of the Curie point and of the spontaneous magnetiza- a neutron diffraction investigated by Bacon and Street [2C] ,
tion. In this case, according to Eq. (2.10), the quantities and also investigations of the antiferromagnetic reson-
a and b can be obtained from the isotherm H/CT = f(cr2), ance, did not confirm the presence of antiferromagnetic
the linear part of which is determined by the coefficient ordering in this compound. This contradiction in the ex-
b. The sign of this coefficient, as already noted, should perimental data has led to various interpretations of the
be negative for first-order phase transitions. nature of the magnetic transformations in MnAs. In
Thus, two independent criteria have been obtained Kittel's theory t l : , the transition at ©i = 313° is regarded
for determining the character of the magnetic phase as a magnetic transformation with inversion of the ex-
transition. One of them is the absolute magnitude of the change interaction, resulting from simultaneous realiza-
parameter r], which is calculated from the experimental tion of exchanges of different types, differing from each
data on the compressibility and on the temperature shift other in magnitude and having different dependences on
of the magnetic transformation with changing pressure, the interatomic distances. In the opinion of Bean and
RodbellC2], the transformation in MnAs at 313°K is a
*As is well known, at the present time the question of the singularities transition from the ferromagnetic to the paramagnetic
of the thermodynamic potential and of its derivatives at a second-order state, and the maximum of the susceptibility at 399°K
phase transition point cannot be regarded as solved, so that the problem is due to the Jahn- Teller effect and is connected with
of the validity of expanding the thermodynamic potential at the second-
order phase transition point should be regarded as open. the structural changes of the lattice. As already indica-
MAGNETIC FIRST ORDER PHASE TRANSITIONS 731
ISO
125
100
75 75
SO 50
25 - 25
0 JO i i 270Z30 310 330.750 370 330 410 430 450 470
70 120 170 ZZO Z7O 3Z0 370 4Z0 470
FIG. 4. Temperature dependence of Youngs modulus E, the shear
FIG. 3. Temperature dependences of the magnetization of MnAs (1) modulus G, the Poisson coefficient n, and the compressibility K of MnAs
and of the reciprocal molar susceptibility (2), measured at H = 10 kOe.
732 N. P . GRAZHDANKINA
to
/?,ohm
35 \
30 II
1\ \
25 - \
h \
\\ \\
\\ \F
V \\
}
\ \
zn zoo zso 300 s/o szo sso I \
T,'K
FIG. 6. Temperature dependence of the induction emf of the meas-
uring coil (relative units)
2
at various pressures.2 1 — Atmospheric pressure,
2 P, kg/cm2
2 - P = 1400 kg/cm , 3 - P = 2350 kg/cm , 4 - P = 2780 kg/cm , 5 - FIG. 8. Dependence of the electric resistance of MnAs on the pres-
P = 2970 kg/cm2. The solid curves were obtained 26
while heating the sure. Measurements in the region of the transition temperature Tc [26].
sample, and the dashed ones while cooling [ ].
MAGNETIC F I R S T ORDER PHASE TRANSITIONS 733
molecular field with a temperature-independent exchange take into account the dependence of the sublattice mag-
interaction, are unable to explain these transformations. netization on the temperature and on the interatomic
Smart'35-1 has shown that for a relative magnetization distances, i.e., he assumes |M^I = |MJJ| = M, and also
ffj in the sublattice j there exist (N/n)(l + <7j) spins ori- that the exchange interactions vary linearly with a, i.e.,
ented in one direction and (N/n)(l — a A spins oriented only the first term is taken into account in the Taylor
in the opposite direction; the entropy of such a system expansion of the exchange energy
is
cubic crystal has an isotropic character and depends of the fact that the signs of the dT s /dP and dT s /dH
only on the volume, then expression (3.3) of Kittel's effects agree with the general thermodynamic relations
theory takes the form V / V T = 1 ± pfC-pM2. The tempera- given above, a difficulty arises in the interpretation of
ture dependence of the thermal expansion, calculated in these effects on the basis of Kittel's theory.
accordance with this formula, agrees qualitatively with The magnetic transformation in Mn3GaC differs from
the experimental data (see Fig. 15). the AF — F transitions in Mn 2 . x Cr x Sb and FeRh in the
c) As shown by Bouchaud and Fruchart [ 6 7 ' 6 8 : , the fact that the change of the spin ordering with increasing
compound Mn3GaC experiences an AF — F transition at temperature at the point T s in Mn3GaC is not accom-
the point T s = 150°K with increasing temperature. panied by an expansion of the lattice (as would be expec-
X-ray diffraction and magnetic measurements have ted from Kittel's theory), but by a strong contraction.
shown that this transformation, as well as the majority In this connection, the experimentally observed negative
of transitions with exchange inversion, is not accompan- values of the dT s /dP and dT s /dH effects do not agree
ied by a change in the crystallographic symmetry with Kittel's formulas (3.6) and (3.7). Pauthenet and
(perovskite-type lattice). The AF —* F transition is a Guillot t69] made an attempt to eliminate these contra-
typical magnetic first-order phase transition, as can be dictions. They also analyzed the AF — F transition on
clearly seen from the temperature and field dependences the basis of the exchange-inversion mechanism of mag-
of the magnetization (Figs. 16 and 17). It was established netic transitions, but took additional account of the
that the transition temperature changes under the influ- ferromagnetic and antiferromagnetic states of the spin
ence of an external magnetic field: dT s /dH = 0.33 entropy in the expression for the thermodynamic poten-
x 10"3 deg-Oe"1 and under the influence of high pressure: tials, and also of the exchange interactions, both inside
dT x /dP = - 2 . 5 1 x 10~3 deg/atm. From these data, on the the sublattices and between the sublattices; this led to
basis of the Clausius-Clapeyron equations a qualitative agreement between theory and experiment.
AV
<?! = (llT,)(dT,ldP)
4. MODELS OF MAGNETIC FIRST-ORDER TRANSI-
and TIONS NOT CONNECTED WITH THE EXCHANGE-
Ao STRICTION MECHANISM
S) (dHsldT)
So far we have considered investigations in which the
they calculated the heat of transition Q in the AF — F magnetic first-order phase transitions were explained
transformation. These two expressions give the closest on the basis of the exchange-striction mechanism.
values Qi = 0.93 and Q2 = 1.02 cal/g. However, in spite There are, however, theoretical papers in which these
transitions are explained with the aid of other model
representations, not connected with the assumption of a
G-cm' strong dependence of the exchange-interaction integral
on the volume of the crystal lattice. Thus, for example,
Yosida and MiwaC70] explain magnetic transformations
of the order-order type, i.e., transitions with inversion
of the volume, occurring in rare-earth elements with
helicoidal magnetic structure, on the basis of the com-
plicated temperature dependence of the constants of the
magnetic crystallographic anisotropy. According to
Dzyaloshinskii l l u , the magnetic structure of rare-earth
metals is determined to a considerable degree by the
shape of the Fermi surface. Transitions between differ-
ent structures are connected with changes of the elec-
tron energy spectrum, which become strong when the
wave vector of the magnetic structure coincides with
Iff - the extremal diameter of the Fermi surface. The source
of all these changes is the temperature dependence of
the parameter of the exchange interaction. In the case
when the exchange parameter has smooth values at which
FIG. 16. Temperature dependences of the magnetizations of the alloy conditions for the existence of the minimum of the
Mn3GaC [68].
thermodynamic potential are violated, jumplike changes
can occur in the magnetic structure, i.e., a first-order
G-cm phase transition.
Karpenko and Berdyshev [72] associate the inversion
of the exchange interaction in antiferromagnetic semi-
conductors of the Lio.iMno.9Se type with the change of the
electric carrier density. In this case it is assumed that
there are two competing types of exchange interactions:
H,iOe an antiferromagnetic interaction of the Kramers type
FIG. 17. Isotherms of magnetization of the alloy Mn3GaC [68]: 1 - (low temperatures) and a ferromagnetic interaction via
T = 146°K, 2 - T = 138°K, 3 - T = 134°K, 4 - T = 121°K, 5 - T = 111% the conduction electrons, the role of which increases
6 - T = 96°K. with increasing temperature as the result of the strong
738 N. P. GRAZHDANKINA
increase of the carrier density. Thus, the effective sign ies in which account is taken of the volume dependence
of the exchange is determined by the relative contribu- of the exchange interactions did not yield positive r e -
tions of interactions with opposite signs. According to sults. It was therefore assumed that the magnetic first-
BlumC73], magnetic phase transitions of the order-dis- order phase transition in the indicated compounds is due
order type can arise in many cases in connection with not to the exchange-striction mechanism, but to some
the special character of the splitting of the electronic other causes.
energy levels, due to the crystal and the magnetic fields. Rodbell, Jacobs, et a.l.l7B1 have shown that if account
The possibility of a first-order transition from the is taken of the biquadratic term in the isotropic indirect
ferromagnetic into the paramagnetic state was indicated exchange during the course of calculation of the tem-
by Shimizu190-1 on the basis of an analysis of the criterion perature dependence of the magnetization in the approxi-
of ferromagnetism in accordance with the band model. mation of the molecular-field theory, i.e., if it is as-
In the opinion of Mitsudo et al. t 7 5 : l , and also of Perm and sumed that the energy of the exchange interaction is of
CohenC76:, first-order transitions in the Neel point of the form
antiferromagnetic metals (e.g., the magnetic trans-
formation in CrC77:i) can be attributed to singularities of /(sV)-/(sV)», (6.1)
the electronic energy spectrum of these metals. The then it is possible to obtain satisfactory agreement be-
hypothesis were advanced that a large influence is exer- tween the calculatedCT(T)curve and the experimental
ted on the character of the magnetic phase transition by data. Anderson :80] first pointed out the possible pres-
the biquadratic indirect exchange in certain antiferro- ence of a term biquadratic in the spins, - j ( s a s b ) 2 , in the
magnetic compounds. [78] expression of the exchange energy, and estimated ap-
In a recently published paper, Bulaevskif and Khom- proximately the magnitude of this term. Later, on the
skii t7 * :i considered, on the basis of the self-consistent basis of an experimental investigation of the paramag-
field method, magnetic transitions in antiferromagnetic netic resonance t81] and a calculation of the interaction
semiconductors (such as V2O3 and Ti2O3[l20~122]) with of the paramagnetic ions in antiferromagnets C82] it was
allowance for the possible excitation of localized elec- also concluded that a biquadratic term must be taken
trons in the conduction band. In view of the strong de- into account in the isotropic indirect exchange. It was
pendence of the energy gap of the electronic spectrum shown there that the ratio j / I is of the order of
of the crystal on its magnetic structure, the magnetic 0.01—0.05. In™ , the temperature dependences of the
transformation is accompanied by an appreciable change magnetic moments of the sublattices of the antiferro-
of the electric properties, namely, when the magnetic magnetic compounds NiO and MnO were calculated on
order vanishes the substance is transformed from a the basis of the theory of the molecular field; no account
semiconductor into a metal. These transformations are was taken of the change in the elastic properties during
first-order phase transitions if the gap in the paramag- the magnetic transformation, and only the change of the
netic state is sufficiently small. exchange energy and of the entropy of the spin system
The influence of the magnetic crystallographic aniso- were taken into account. Allowance for the biquadratic
tropy on the magnetic transitions with exchange inver- term in the exchange energy leads to a change in the
sion were considered in many papers, and were dis- form of the temperature dependence of the magnetiza-
cussed in detail in the monograph of Belov, Belyanchi- tion in accordance with the formula
kova, et al. I 7 9 ] , so that we shall not concern ourselves
with these questions here. We shall dwell only on model (6.2)
representations of first-order magnetic transitions of
the order-disorder type, which are not connected with where
SNksa
the exchange-striction mechanism. F(o) = - OS*
"*" ' da
here S* is the entropy of the spin system, ji and j 2 are
6) Biquadratic Indirect Exchange and Magnetic Trans-
the parameters of the biquadratic exchange with the
formations in Certain Antiferromagnetic Compounds first and second coordination spheres, respectively, and
Neutron-diffraction investigations of the antiferro- I2 is the exchange parameter with the second coordina-
magnetic compounds NiO and MnO have shown that the tion sphere in the bilinear term of the Hamiltonian
change of the magnetization with temperature in the I(s a s b ). Figure 18 shows the dependence of a on T / T J J
region of the Neel point does not follow the Brillouin for NiO, calculated in accordance with formula (6.2)
function: the a(T) curve is steeper, and the magnetiza- under the assumption that Ii = I2 = I and ji = j 2 = j l 7 9 2 .
tion jumps down to zero in the immediate vicinity of TJJ. Agreement with the experimental data is obtained when
In this connection, it was proposed that the transition j / I = 0.015 for NiO and j / I = 0.02 from MnO. From the
from the antiferromagnetic into the paramagnetic state plots of Fig. 18 we see that the magnetization in the
in these compounds is a first-order phase transition. A region of the Neel point changes sharply when the tem-
characteristic and very significant feature of the des- perature changes, and the character of this change
cribed phase transitions is the sharp change of the elas- corresponds to a first-order phase transition. In the
tic constants of the crystal in the absence of any volume case when j = 0, i.e., when no account is taken of the
changes in the region of the antiferromagnetic trans- biquadratic indirect exchange, calculation in accordance
formation. The effects of the shift of the transition tem- with (6.2) leads to the usual dependence of the magne-
perature with changing pressure are relatively small in tization on the temperature, corresponding to the Brill-
these compounds. An attempt to calculate the jump of ouin function, and consequently to a second-order mag-
the magnetization at the Neel point on the basis of theor- netic phase transition (dashed curve of Fig. 18).
M A G N E T I C FIRST ORDER PHASE TRANSITIONS 739
F I G . 2 2 . D e p e n d e n c e of t h e free e n e r g y o n t h e m a g n e t i z a t i o n in ac-
c o r d a n c e w i t h B l u m ' s calculation [73]. First-order phase transition for
T = 0.786.
0 IB ZO 30 W 50
T,°K
MAGNETIC FIRST ORDER PHASE TRANSITIONS 741
• 0. (8.6)
dM-
FIG. 24. Temperature dependence Following the Weiss hypothesis, it can be assumed that
of the elastic constants of UO2 in the the dependence of the exchange energy on M is given by
region of the antiferromagnetic trans- £ex -,-|ttJtf ! ; (8.7)
formation.
and then
HL ^ - aM and tfl-E
dM
taking (8.4) into account, we can conclude that E = 0 when
M = 0. Inasmuch as the total energy should be negative
0 W SO ISO WO ZOO ZW following ferromagnetic ordering, it is necessary to de-
T,°K termine the condition when E < 0 for M * 0. To analyze
the relations between E, E^, E e x , a, and M leading to a
cular field, and equal to the reciprocal of the paramag- stable ferro- or paramagnetic state, Shimizu used a
netic susceptibility of the electron gas at 0°K graphic method. Solving (8.4) by integrating by parts:
(a" 1 = Xo(0)). Attempts were made subsequently to de- El £0
termine the conditions for the occurrence of ferromag- E = G,-t,t)n- U1(e)dE-W2(e)d8 + £ e x , (8.8)
netism in a system of collectivized electrons with arbi- to £2
trary dispersion law, i.e., for an arbitrary band, when and plotting n against AS to correspond to the investiga-
the v{t) dependence can have an arbitrarily complicated ted density of states curve, he determined the change of
form. In an extensive investigation, Shimizu has the total energy, and also of the individual contributions
shown [90'9i:l that the ferromagnetism criterion in the Efc and E e x , as functions of the magnetization of the sys-
band model depends on the general topology of the den- tem. Figure 26 shows the change of n (number of singly
sity of states, the position of the Fermi level, and the occupied levels) for various values of the widths of the
magnitude of the molecular-field coefficient. It was es- energy band near the Fermi level; it is seen from this
tablished there that in a number of cases, when the figure that for the case when n = n' and AS = £1 - £2, the
Fermi level lies near the minimum of the density of area OG3G2F2n'O, between the curve and the ordinate
state curve, the transition from the ferromagnetic into axis is equal to the change of the kinetic energy deter-
the paramagnetic state can be a first-order phase tran- mined by the sum of the first three terms of (8.8). Tak-
sitions. ing into account (8.3), (8.5), and the functional depen-
In Shimizu's cited papers C9O'91], he investigated the dence of the exchange energy on the magnetization (8.7),
dependence of the kinetic and exchange energies on the we can determine the relation between A£ = 9E ex (n)/Sn
spontaneous magnetization of the system of electrons. and n (the straight lines OF 1; OF 2 , OF 3 , OF 4 , and OF 5 on
Figure 25 shows the change of the density of states as a Fig. 26), and also the absolute value of the exchange en-
function of the energy at 0°K. Here £0 is the Fermi ergy E e x , which equals the area between the indicated
level for the paramagnetic state and Vi(e) and v2(t) are straight lines and the ordinate axes. For the case
the density of states for e > £0 and e < £0, respectively. A£ = £1 - £2, this is the area OF 3 n'O. If the change of
The number of singly-occupied levels n(£), both above the kinetic energy is smaller than the contribution due to
and below the Fermi level, is the exchange energy E e x (the area OG3FiF2F3n'O is
smaller than the area OF3n'O), then the total energy is
) = I v, (e) de, n2 (y = § v2 (e) de. (8.1) negative and the system is in the ferromagnetic state.
If the change of Ej^ is exactly equal to the change of E e x ,
Depending on the form of the v(e) curve, the values of then the indicated two areas are equal and the state of
ni(£i) and n2(£2) differ. When spontaneous magnetization the system can be characterized as critical. For the
M occurs, some of the electrons occupying states below paramagnetic state, the total energy should be positive,
£o go over into states above £0, and then and consequently E^ must be larger than E e x . The de-
pendence of E on M for all the cases indicated above is
(8.2) shown in Fig. 27. An analysis of the change of the coeffi-
M = 2pBn. (8.3)