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Magnetic interactions in gadolinium orthochromite, GdCrO3

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1974 J. Phys. C: Solid State Phys. 7 3133

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J. Phys. C : Solid State Phys., Vol. 7, 1974. Printed in Great Britain. 0 1974

Magnetic interactions in gadolinium orthochromite, GdCr03

A H Cooke, D M Martin? and M R Wells

Department of Physics, Clarendon Laboratory, Oxford

Received 4 March 1974

Abstract. The magnetic properties of the distorted perovskite G d C r 0 3have been investigated
by magnetic moment measurements in the temperature range below 100 K and specific heat
measurements below 10 K. Earlier workers have shown that at 170 K the Cr3+ions order in
a G,F, configuration (in Bertaut's notation). Our measurements show that the canting of the
Cr3'. ions from a simple antiferromagnetic alignment is due to antisymmetric exchange
coupling between Cr ions. The value of the weak ferromagnetic moment F, is 400 emu mol-'.
The interaction between the Cr3+ and G d 3 + ions produces an effective field at the Gd sites
of 5.5 kOe, acting in the opposite direction to F,. This effective field is attributed to high-order
anisotropic exchange interactions.
At a temperature of approximately 7 K the Cr-Gd interaction is sufficient to cause the Cr
system to undergo a spontaneous spin reorientation from a G,F, to a G,F, mode, which is
observed in the specific heat as an anomaly.
At 2.3 K the interaction between the Gd3+ ions is sufficient to bring about a co-operative
transition to an antiferromagnetic state indicated by a i-anomaly in the specific heat. Our
measurements do not allow a precise determination of the ordered state of the Gd ions except
to indicate that they are confined to the basal plane.

1. Introduction

The rare earth orthoferrites and orthochromites (RFeO, and RCrO,, where R is a tri-
valent rare earth or yttrium) have proved in recent years an interesting series of com-
pounds for investigations of various types of magnetic interactions in solids. This paper
gives an account of investigations into the interactions in gadolinium chromite, GdCrO,.
by magnetic moment and specific heat measurements. In this compound three different
types of interaction have to be considered, namely the Cr-Cr, Cr-Gd and Gd-Gd
interactions, but because their magnitudes differ considerably their effects can be sepa-
rated by measurements in different temperature ranges. Above about 100 K the Cr-Cr
interaction predominates in determining the magnetic properties, producing magnetic
ordering of the Cr system at 170 K. Below 100 K the effects of the Cr-Gd interaction
become increasingly important, while at temperatures in the liquid helium range account
must be taken of the Gd-Gd interaction. which produces ordering of the Gd system at
2.3 K. The approach adopted in this paper is to describe the effects of these interactions
in turn.
+ Present address. Hyde County Grammar School, Hyde, Cheshire

3133
3134 A H Cooke, D M Martin and M R Wells

The magnetic properties of the isomorphous GdFeO, have been reported previously
in the paper by Cashion et a1 (1970), which also discusses the experimental equipment
used to obtain the results described here.

2. Structure and symmetry properties

GdCrO, has been shown to crystallize in a distorted perovskite structure, space group
Pbnm (Geller 1957). This structure is shown in figure 1, the oxygen ions having been
omitted. The dimensions of the orthorhombic unit cell are a = 5.312A, b = 5*514A,
c = 7.611 A. whilst the angle p, shown in figure 1, in the monoclinic cell is 91.1: The Cr

axis)

Figure 1. The crystal structure of GdCrO,: 0 represent Gd atoms and 0 represent Cr atoms.

ions lie on undistorted positions relative to the orthorhombic cell, whilst the Gd ions are
slightly removed from the special positions they are shown to occupy in figure 1 by an
amount parametrized by the numbers U and D. The coordinates of the rare earth and Cr
sites, numbered 1-4 in figure 1, are given in table l(a). In GdCrO, the parameters U and U
are unknown. However Geller and Wood (1956) have deduced that U = -0.018, 1) =
0.06 in isomorphous GdFeO,, and it will be assumed that these values are also applicable
to GdCrO,. It should be noted that although the Gd ion positions are slightly displaced
in the ab plane, they lie on a mirror plane perpendicular to the c axis. This has important
consequences in the discussion of the Gd-Cr interaction.
The allowed magnetic ordering arrangements for the Cr and Gd sites have been
worked out by Bertaut (1963) under the assumption that the magnetic and crystalline unit
cells are identical. Considering the spin components along a particular crystal axis, the
four possible ordering patterns are those shown diagrammatically in table l(b). (For
example, if we consider the spin components along the a axis, an ordering in which the
spin components of all four ions along this axis were parallel would be labelled F,, while
if the spin components of ions 1 and 2 were parallel, but antiparallel to those of ions 3 and
4. it would be labelled Cx.)From symmetry considerations, Bertaut has shown that the
arrangements of spin components along the three principal axes which can exist together
 Magnetic interactions in GdCrO, 3135

Table l(a). lon positions in the Perovskite structure

Table l(b). Schematic representation of the four spin modes, F , G, C and A

o +-spin
spin I7 !Il a El
F G C A

Table l(c). Representations of the allowed ordering modes for Cr ions

r, Ax G, c,
rz F, c, G,
r3 c, F, A,
r4 G, A, F,

Table l(d). Representations of the allowed ordering modes for Gd ions

are for the Cr ions those listed in table l(c), and for the Gd ions those listed in table l(d).
When we consider simultaneous ordering of both the Cr and Gd systems, only ordering
modes belonging to the same representation can couple together. It should be noted
however that this restriction depends on the assumptions that the magnetic and crystalline
unit cells are identical, and that the ordering has not been accompanied by a distortion
lowering the symmetry.
The crystals used in the measurements were flux grown by Mrs B M Wanklyn, and
details are given in Wanklyn (1969). Crystals of this structure tend to grow with natural
faces corresponding to the faces of the pseudocubic cell. For the magnetic measurements
a single crystal was chosen for which the angle fl could be unambiguously identified; it
had a mass of 133 mg and dimensions 2.2 x 2.7 x 3.3 mm. In addition 6.5 g of clean
crystal were available for specific heat measurements. Electron probe microanalysis of
the single crystal indicated that the impurity content was less than 1% (0-7-0.8 % Pb).
3136 A H Cooke, D A4 Martin and M R Wells

3. The chromium ordering process

It has been shown by Aldonard et a1 (1966) that the Cr system in GdCr0, orders anti-
ferromagnetically at a temperature of 170K (TN1).In addition a weak ferromagnetic
component is observed below this temperature due to the fact that the Cr moments are
canted out of true antiferromagnetic alignment. Magnetic moment measurements below
TN,show that this weak ferromagnetic moment lies parallel to the crystallographic c axis.
Group theoretical considerations (Bertaut 1963) then show that the crystal symmetry
restricts the Cr ordering arrangement to A,G,F, in the Bertaut notation. Neutron
diffraction results obtained by Mareschal and SivardiBre (1969) showed that in some
other members of the rare earth orthochromites studied by them the ordering mode
of the Cr system was GJ,, and it will be assumed that the ordering mode of the Cr system
in GdCr03 is GJ,. thereby neglecting any A, component.
On the basis of an isotropic Heisenberg Hamiltonian of the form A? = - 2JQ, . QJ,
where Q refers to the Cr spin vector, Van der Ziel and Van Uitert (1969) give an average
value of J / k of 12.7cm- ' for the interaction between neighbouring Cr ions in GdCrO,.
On a molecular field basis this can be related to a fictitious exchange field by the formula
J l k = gPHE/2zkQ, where z refers to the number of interacting nearest neighbours (six,
in this case). Thus HE = 1.2 MOe.
The canting of the Cr moments out of true antiferromagnetic alignment is due to the
effects of an antisymmetric exchange interaction which prefers interacting spins to align
themselves perpendicular to each other. This effect has been formally shown by Moriya
(1960. 1963) to arise out of the introduction of spin-orbit coupling as a perturbation on
the quenched Cr3+ ground state. The appropriate term in the Hamiltonian can be
written D. Q, x QJ, whilst its effect within the crystal can be phenomenologically
described in terms of the so-called Dzialoshinski field (H,) acting in the direction of the
weak ferromagnetic moment, Its magnitude in G d C r 0 3 can be derived by a simple
proportionality argument. It will be shown later that the magnitude of the canted Cr
'.
moment is 400 emu mol- Thus :

Now Q = 2 and HEhas been given previously. thus H , = 60 kOe. ( 5 % of HE). This
can be compared with the value of H , = 70 kOe given for the Cr system in YCrO, by
Judin and Sherman (1966).

4. The Gd-Cr interaction

The ordered Cr system produces an effective internal field (HI)at each Gd site. This field
will induce a magnetization of the rare earth ions even in zero applied magnetic field. In
this section it will be assumed that our measurements were made at temperatures
sufficiently far below TN1for the Cr ion moments to be fully aligned into sublattices. The
value of HI should thus remain constant with temperature (neglecting any possible
reaction of the magnetization of the Gd system on the canting of the Cr system).
Figure 2 shows the results of magnetic moment measurements carried out in applied
fields up to 1.5 kOe parallel to the c axis at the temperatures specified on each curve. The
values of applied field have been corrected to those appropriate to a needle-shaped
 Magnetic interactions in GdCrO, 3137

3 x 10' 14 K

I --

H, (kOe)
-I
+

Figure 2. The magnetic moment of GdCrO, in emu mol-' against magnetic field in kOe
applied parallel to the a axis, as a function of temperature.

specimen of zero demagnetizing factor. Although for temperatures 105 < T < TN1a
true zero-fieldmoment is observed in the z direction, this disappears below 105 K, and
instead there is a high initial increase in moment, on the application of a low ( - 100 Oe)
magnetic field. This is attributed to the formation of magnetic domains, once the magni-
tude of the zero-field moment exceeds a certain value.
The appearance of these moment curves can be explained on the basis of the following
model. If we assume that in addition to the applied field Ha,an internal field HIdue to the
Cr system is acting along the c axis at each rare earth site, then the measured moment M ,
is related to the canted moment of the Cr system M,, by the formula:
M = Mc, + CGd(H1 f HJ/(T + 0). (1)

Here we have assumed that the susceptibility of the Gd system follows a Curie-Weiss
law, with Curie constant CGd(theoretically equal to 7-875for the 8S,,2Gd3fground state)
and Weiss constant. U , and also that the applied field Ha does not appreciably change the
moment of the Cr system.
From (1)it can be deduced that if H,= -Ha, then M = Mc,, and one would expect
the curves to intersect at a common point, irrespective of temperature. This is seen in
figure 2. the intersection point being ( - 400 k 25 emu mol; - 5.5 k 0.2 kOe.) Thus the
value of the canted moment of the Cr system is Mcr = 400 emu mol; whilst the internal
field at the Gd sites is H , = 5.5 kOe, in a direction opposite to that of the moment Mc,.
The signs emerging from this analysis are important, and indicate that at these tempera-
tures the situation is as shown in figure 3 ; that is, the moment measurements were taken
below the compensation point, at which the canted Cr moment and the moment induced
in the rare earth system by the field H I are equal and opposite. Equation (1) leads to an
estimate of the compensation point of 110 K. In addition the Gd system is found to follow
a Curie-Weiss law of the form XGd = 8.1/(T + 2.3).
Magnetic moment measurements parallel to the a axis in applied fields up to 10 kOe
3138 A H Cooke, D M Martin and M R Wells

Figure 3. The two canted chromium sub-

lattices give a net moment McT.This produces
an effective field H , at the gadolinium sites,
inducing a paramagnetic moment M,,due t o
the gadolinium ions. Below the compensation
temperature, M,, exceeds Mer, so that when
an external field H , is applied; the direction of
the chromium moment M,, is opposite t o
that of the applied field.

in the liquid hydrogen temperature range reveal an interesting effect. This is shown in
figure 4 where the applied field has been corrected for the finite demagnetizing factor of
the sample. Initially the magnetic moments are proportional to the applied field but at
about 2 kOe the behaviour changes and above this field the magnetization curves are the
same as those observed for fields applied along the c axis with a common intersection
point. This effect can be explained in the following way.
The effective Cr anisotropy field which leads to a preference for G,F, over G,F, must
be quite small (-2 kOe). When an external field is applied along the a axis, the Cr
moments begin to rotate in the ac plane until at about 2 kOe a G,F, mode is induced.
Thereafter equation (1) can be applied. This gives M,, = 500 ? 50emumol-' and
H , = 6.4 f 0.5 kOe, values comparable with those for the G,F, mode. (In comparing
the two sets of values it must be remembered that the measurements along the a axis
required the use of applied fields up to 10 kOe, or about 15 % of the Dzialoshinski field.
The assumption that the applied field does not appreciably change the value of the Cr
moment is therefore more questionable than for the measurements along the c axis.)
In applied fields up to 20 kOe along the b axis the susceptibility was found to follow a

xlO3 6~ 9,14 K

Figure 4. The magnetic moment of GdCrO, in emu mol-' against magnetic field in kOe
applied parallel to the a axis, as a function of temperature.
 Magnetic interactions in GdCrO, 3139

Curie-Weiss law, x = %5/( T + 2.3).No zero-field moment, either real or by extrapolation

from the high-field results, was observed at any temperature. This is not surprising when
one considers the form of the D Q ix Q, interaction. It can be shown from symmetry
arguments that the D vector points in a direction parallel to the b axis. Thus in the absence
of an external field the Cr spins must be confined to the ac plane.
It will be seen that our results are entirely consistent with the hypothesis that in the
orthochromites the canting of the Cr system arises from the Dzialoshinski-Moriya
interaction. If instead the canting arose from crystal-field effects. as in NiF2, we would
expect that the direction of the canted moment would be fixed, instead of being readily
rotated in the ac plane.
The fact that the anisotropy in the ac plane is small has another important consequence
which will be discussed below, namely the possibility of a spin reorientation in zero field
at low temperatures.

5. Origin of the internal field H , .

In discussing the internal field HI produced at the gadolinium sites by the ordered chro-
mium system, it is convenient to consider separately the effect of the x components Q,
of the chromium spins, which form a two-sublattice antiferromagnetic array. and the
effect of the z components Qz, which form a ferromagnetic array whose moment is very
small compared with the saturation moment of the chromium system, (less than 3 %).

5.1. Magnetic dipole interaction

Computation of the appropriate dipole sums allows this to be calculated precisely. The
contribution due to the moments Q, is negligibly small (2 Oe). The moments Q, yield an
interaction field HI of 470 Oe directed along the z axis. Thus the field due to magnetic
dipole interaction is an order of magnitude too small to account for the observed HI.?

5 2. Isotropic exchangt. interaction

It has already been mentioned that the Gd ions lie on mirror planes perpendicular to the
c axis. Because of this the interaction due to the antiferromagnetic array of the compo-
nents Q, vanishes. since the effects due to pairs of Cr ions above and below the plane
exactly cancel.
Isotropic exchange between the gadolinium ions and the components Q , could in
principle contribute appreciably to H,, but the following argument suggests that it is
small. The results presented in figure 2 show that down to 14 K the moment M c r and
the interaction field H , are independent of temperature, while the moment M,;of the
gadolinium system increases as the temperature falls. Now if the interaction between the
two systems arose from isotropic exchange, we could write its energy as E = - rMCrMGd.
where Y is a constant. Then HI = aMc,. Since HI = 5.5 kOe and Mcr = 400 emu mol- ',
this gives r = - 14. This implies a 'reaction field' at the chromium ions of magnitude
YM,,, and as the temperature is lowered and MGd increases, this field would increase
until at 14 K. at which M,, = 2400 emu mol- iit would amount to 34 kOe. Such a field
I' In an earlier paper on GdFeO, (Cashion et al 1970) it was wrongly assumed that this contribution to the
interaction field would vanish by symmetry In fact the calculated value for GdFeO, is 780 Oe, a value somewhat
greater than the very small interaction field (310 Oe) found experimentally for this compound
3140 A H Cooke, D M Martin and A4 R Wells

would be comparable in magnitude with the Dzialoshinski field, estimated to be 60 kOe.

which is responsible for the canting of the Cr system, and so should cause Mcr to increase
as the temperature is lowered. Since in fact Mcris found to be independent of temperature,
we conclude that isotropic exchange does not contribute significantly to HI.

5.3. Pseudodipolar and antisymmetric exchange interaction

Having eliminated magnetic dipole and isotropic exchange interactions between the
Cr3+ and Gd3+ions, we are led to conclude that the internal field acting on the Gd ions
arises from an interaction involving the product of Q, and S,. Moriya (1960) has shown
that couplings involving such products can arise from antisymmetric exchange or from
pseudodipolar coupling. These are high-order interactions which arise from the effect
of spin-orbit coupling, introduced as a perturbation on the spin-only ground state of the
magnetic ions. It is not possible to give a quantitative estimate of their magnitudes, but a
comparison between GdFeO, and GdCrO, is interesting. In an order-of-magnitude
argument, Moriya suggests that antisymmetric exchange will be proportional to Ag/g,
and pseudodipolar coupling to (Ag/g)? where Ag is the departure of the observed g value
from the free spin value, 2,002, this being a crude measure of the departure from spin-only
behaviour. Paramagnetic resonance measurements on a wide variety of compounds
give for Gd3+the value g = 1.99,for Cr3+values 1.97-1.98, but for Fe3+the values found
are very close to the free spin value. We may then expect that these interactions, and
especially pseudodipolar coupling, will be much smaller in GdFeO, than in GdCrO,,
and this accords with the observation that in GdFeO, the effective field on a Gd ion is
only 310 Oe, as against 5 500 Oe in GdCr03.

6. Spin reorientation

The measurements above 14 K illustrated in figures 2 and 4 show that although in zero
applied field the Cr system is ordered in a G,F, mode, a F,G, mode can be induced by the
application of a field of some 2 kOe along the a axis. Figure 5 shows the analogous curves
at 4.2 K. One can immediately see that the rdes of the a and c axes have been reversed.
The high initial slope previously observed along the c axis is now apparent along
the a axis, while a field of approximately 0.5 kOe along the c axis is required to reintroduce
a G,F, mode at 4.2 K. It is found that as the temperature is lowered below 4.2 K this field
increases until at 0.5 K q field of 2.5 kOe along the c axis is required to effect the reorien-

H, (kOe)
Figure 5 . Comparison of the magnetic moment in emu mol-' along the a and c axes as a
function of magnetic field in Oe at a tempeature of 4.2 K A a axis: 0 c axis.
 Magnetic interactions in GdCr03 3141

tation. One is therefore led to the conclusion that a zero-field spin reorientation of the Cr
moments from the high-temperature G,F, mode to aF,G, mode occurs in the temperature
range 4.2 < T < 14 K.
This phenomenon of spin reorientation is well known in the orthoferrites and
orthochromites. At high temperatures the configuration of the Cr system is determined by
crystalline anisotropy, which in GdCr03 favours the G,F, mode. As the temperature is
lowered, the interaction of the Cr and rare earth moments becomes important, and may
overcome the crystalline anisotropy forces.
Sivardiere (1969)has given a simple theory of spin reorientation for a system in which
the magnetic behaviour of the rare earth ions is highly anisotropic. The magnetic proper-
ties of the Gd ions are very nearly isotropic, but an order of magnitude calculation can be
given as follows. The anisotropy energy associated with the reorientation of the chromium
system is of the order of lo6 erg mol-' (AE/R 0.01), since our measurements in the
N

hydrogen temperature range show that an external field of 2 kOe acting on the ferro-
magnetic moment of the Cr system ( 5 0 0 emu mol-') produces reorientation from G,F,
to F,G,. This energy has to be compared with possible anisotropy in the interaction
energy of the Cr and Gd systems, ;xGdHEas the direction of H,rotates from the c axis to
the a axis. We have H , = 5.5 kOe. and zc,d = 8/(T + 2). so that at 6.5 K (the reorientation
temperature indicated by our specific heat results below) the interaction energy is approxi-
mately 1.4 x lo7 erg mol-' ( E / R 0.2). Thus a small anisotropy in zGdor HI would
N

suffice to favour reorientation of the Cr system below a certain temperature. Crystalline

electric-field effects could produce anisotropy of the required order, and we consider
therefore that the spin reorientation observed in GdCr03 arises from the effect of com-
petition between the anisotropy field acting on the Cr ions and their interaction with the
Gd ions.

7. The Gd-Gd interaction

Figure 6 shows the molar specific heat of GdCrO, in the temperature range 0.5 < T <
10K. A lattice contribution varying as 6.7 x lo-' T 3 has been subtracted. This was
derived from a plot of C T 2 / Ragainst T 5in the region 3 < T < 8 K, under the assump-
tion that a T 3 relationship is followed.
2O r

I
2 4 6 a IO
T (K)
Figure 6. The molar heat capacity of GdCrO, in the temperature range 0.5 K to 10 K.
3142 A Ei Cooke, D M Martin and M R Wells

The results show two features, the anomaly having a sharp peak at 2.3 K and the
much smaller anomaly at 6.5 K, which we attribute to the spin reorientation discussed in
the previous section. The energy associated with this anomaly is AE/R = 0.02 K in
agreement with the order of magnitude calculation already given. The much larger ano-
maly at 2.3 K is ascribed to the co-operative magnetic ordering of the Gd system brought
about by the Gd-Gd interactions. The overall shape of this anomaly bears a resemblance
to the usual R-anomaly observed in the co-operative ordering of magnetic systems, but
with a very broad tail on the high-temperature side, which can be explained by the
perturbing influence of the internal field HI, which produces an overall splitting A =
14PH, in the Gd3’- *S, ground state. where A/k = 5.2 K. Measurement of the total
entropy associated with the anomaly at 2.3 K gives a value (2.08 k O.l)R,in good agree-
ment with the value R log (2s + 1) = 2.08 R for a system with S = ;.
Difficulty is experienced in attempting to deduce either the Gd ordering direction or
the ordering arrangement below TN2.In a simple two-sublattice antiferromagnet,
susceptibility measurements are invaluable in determining the ordering direction, since
the susceptibility xl, in fields along the alignment axis falls rapidly with temperature
below T,. while the susceptibility xi perpendicular to the axis remains constant. Suscepti-
bility measurements on GdCrO, show that in no direction does the susceptibility tend
to zero as the temperature is lowered below TNz.suggesting that the ordered state is not
a uniaxial two-sublattice system. A similar problem was encountered in the case of
GdFeO, (Cashion et a1 1970). The most useful information concerning the ordering is
obtained from high field magnetic moment measurements at 0.5 K. These are shown in
figure 7 for fields applied along the a, b, and c axes. The fields have been corrected to allow
for the finite demagnetization factor of the sample. Since T < TN2,it will be assumed that
the Gd ion moments are fully aligned into sublattices
Examining figure 7, we note first that for all three directions saturation is reached at
sufficiently high fields, the saturation moment being 38000 emu mol-’ (6.8 pB per Gd ion).
For an assembly of Gd3’ ions the saturation moment is 39 100 emu mol- (7 pB).This
discrepancy of 2.5 % is not considered significant ; the accuracy of our moment measure-
ments is estimated to be 1 %, and as already noted the specimen contained 1% impurity.
In high fields. the rate of approach to satbration is the same for all three directions, corres-
ponding to a differential susceptibility xhl = 1.53 mol- ? We take this to be the value of
for the ordered Gd system.
x1044r

3
-h
-
E
$ 2
v

2
I

IO 20 30 40 50
Hc (kOe)
Hb
Eigure 7 The magnetic moment in emu mol- I as a function of magnetic field in kOe’ for the
three oithorhombic axes at a temperature of 0 5 K A a axes 0 b axis 0 c axis
 Magnetic interactions in GdCrO, 3143

For fields along the c axis. saturation is approached at a uniform rate, except for an
abrupt discontinuity of 8000 emu mol-' at a field of 2.5 kOe, which we attribute to the
rotation of the Cr system from the G,F, to the G,F, mode, resulting in a sudden increase
in the field in the z direction at the gadolinium sites. Back extrapolation of the linear
portion of the curve above 2.5 kOe gives a value of 5.8 kOe, in reasonable agreement with
the estimate H,= 5.5 kOe from the high-temperature measurements. When account is
taken of this. one sees that the Gd moment increases linearly with field right up to
saturation. This is the behaviour to be expected if the c axis is perpendicular to the plane
in which the Gd sublattices lie, and we therefore suggest that the ordered state is such that
in zero applied field the Gd sublattices lie in the ab plane.
In considering the measurements in fields applied along the a axis, it must be
remembered that even in zero applied field the Cr system produces an internal field at
the Gd sites along this axis. Application of a small external field to overcome domain
effects gives a 'zero-field' moment of 4700 emu mol- i As the field is further increased, the
initial slope of the curve of moment against field corresponds to a differential suscepti-
bility x, = 0.65 mol-', that is a smaller value than 1, (1.53 mol-'). At fields near 7 kOe
the moment increases more rapidly, in a way characteristic of a spin-flop transition, and
then rises linearly U ith field at a rate corresponding to a differential susceptibility x =
1.53 mol- '.
In fields applied along the b axis the moment first rises with field at a rate corres-
ponding to a susceptibility xb = 1.25 mol-', with again an increase, tentatively ascribed
to spin-flop, at fields of about 8 kOe. Above 10 kOe the moment rises linearly with field,
at the same rate as along the a and c axes, as is to be expected above a spin-flop transition.

8. Conclusion

In GdCrO, the Cr3' ions form a canted antiferromagnetic array, G,F,. Our experiments
show that the canting of the Cr3+ions is due to the Dzialoshinski-Moriya antisymmetric
exchange interaction between the Cr3 ions. The Cr-Gd interaction causes a spontaneous
+

spin reorientation of the ordered Cr system from G,F, to G,F, at approximately 7 K.

producing a small anomaly in the specific heat.
At 2.3 K the Gdj' ions undergo a transition to a canted antiferromagnetic state, with
a ferromagnetic moment F , = 4700 emu mol-'. If the magnetic unit cell coincides with
the crystalline unit cell. only an F,C, ordering of the Gd system can be coupled with the
F,C, ordering of the Cr system since both must belong to the same representation, Tz
(see table 1). However other possibilities are that the ordering of the Gd ions is accom-
panied by a crystalline distortion (Yamaguchi and Tsushima 1973), or that the magnetic
unit cell comprises more than one crystalline unit cell. Neutron diffraction studies are
ruled out by the high-absorption cross section of gadolinium. Magnetoelectric measure-
ments should throw some light on the question since, for example, the magnetoelectric
effect would vanish for a magnetic unit cell comprising two crystalline cells, and work on
this is being put in hand.

Acknowledgments

The authors would like to thank Mrs BarbaraM Wanklyn, ofthis Laboratory, for growing
the crystals of GdCrO,. Assistance in the Electron Probe Microanalysis of the single
3144 A H Cooke, D M Martin and M R Wells

crystal sample by the Metallurgy Department, University of Oxford, is gratefully ack-

nowledged. The work was carried out during the tenure by one of the authors (DMM)
of an SRC grant.

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Geller S 1957 Acta Crystallogr. 10 243-51
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Judin V M and Sherman A B 1966 Solid St. Commun. 4 661-3
Mareschal J and Sivardiere J 1969 J . Phys., Paris 30 967-73
Moriya T 1960 Phys. Rev. 120 91-8
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