M A G N E T I C P H A S E T R A N S I T I O N IN MnSO 4

E. L E G R A N D , S. H A U T E C L E R , W. W E G E N E R and G. W I L L *
S C K / CEN, B-2400 Mol, Belgium

After the magnetic structure of m a n g a n o u s sulfate had been determined by Will et al., Solyom concluded from theoretical
considerations that the structure could only arise following three successive phase transitions. Neutron diffraction measurements
performed at various temperatures are in full agreement with these theoretical conclusions.

The magnetic structure of MnSO4, as determined
by Will et al. [1], consists of a conical spiral
arrangement with the cone axis parallel to the c-
axis. The magnetic moments at sites ( x , y , 0) are
antiparallel with those at ( x , y , l); the z compo-
nents form a collinear antiferromagnetic structure
while the projections on the a - b plane cycles in
this plane, the propagation vector of this spiral
component being parallel to the a-axis.
Solyom [2] could show from theoretical consid-
erations that this conical magnetic structure can
appear only in three successive steps. Not only the
antiferromagnetic z component and the spiral com-
ponents in the a - b plane should order at different
temperatures but also the ordering of the x and y
components should not happen at the same point.
In addition to this, he also concluded that an
oscillatory component in the z direction must be
In fig. 1 the temperature dependence of the
(001) -+ satellite (circles) and the (001) ° reflection
(squares) are shown. Due to background uncer-
tainty the intensities at 10.8 and 12.7 K could not
be fitted and the open squares gives the estimated
intensities. The crosses on the abscissa indicate
the temperatures at which anomalies were found in
the specific heat measurements. If we extrapolate
the temperature dependence of the satellite peak
intensities (as shown by the dashed lines) we find
that the transition temperature of the satellite peak
as well as the anomaly in its temperature behaviour
coincides very well with the anomalies in the
specific heat data.
The three transitions, predicted by Solyom, are
found both in neutron diffraction and in specific
tO

present and the spiral structure should be elliptical.

Experimental evidence for the three phase tran-
sition has been obtained from specific heat
measurements, where three anomalies were found
at 7.2, 10.5 and 11.5 K [3].
Our neutron diffraction measurements, per- 150001
formed at 4.2 K with a wavelength of 2.569 A,
showed clearly that besides the satellite peak
(001) -+ a (001) ° contribution is also present. This
indicates that the collinear antiferromagnetic com-
ponent of the magnetic m o m e n t must have a non-
10000 i,
zero projection on the a - b plane. The general
aspect of the magnetic structure remains un-
changed but the cone axis must be inclined with
respect to the c-axis. From the measured intensities
5000 ',
we obtained the following results: the magnetic
moment /~ = 4.8 /~B; the cone axis lies in the a - c
plane making an angle of 7 ° with the c-axis; the
cone half angle is 71.5 ° . 5 10 1'5K~
Fig. 1. Intensities at different temperatures of the satellite com-
*Mineralogisches Institut der Unlversit~t Bonn, Lehrstuhl fiir ponent (circles) and the collinear c o m p o n e n t (squares). The
Mineralogie und Kristallographie, D-5300 Bonn, Fed. Rep. crosses on the abscissa indicate the temperatures at which
Germany. anomalies were found in the specific heat measurements.

Journal of Magnetism and Magnetic Materials 15-18 (1980) 529-530 @North Holland 529
530 E. Legrand et al./ Magnetic phase transition in MnSO4
h e a t m e a s u r e m e n t s . T h e collinear a n t i f e r r o m a g -
netic c o m p o n e n t o r d e r s first at 11.5 K. A t 10.5 K
the x or y c o m p o n e n t of the spiral b e c o m e s
o r d e r e d a n d at 7.2 K the spiral is c o m p l e t e l y
o r d e r e d . F r o m o u r m e a s u r e m e n t s we can not con-
clude w h e t h e r the x or the y c o m p o n e n t o r d e r s
first. But since the position of the satellite p e a k
does not change in a m e a s u r a b l e way, the p e r i o d i c -
ity of the spiral c o m p o n e n t a p p e a r s to be essen-
tially t e m p e r a t u r e i n d e p e n d e n t . T h e fact that the
cone axis does not c o i n c i d e with the c-axis explains
the two o t h e r c o n c l u s i o n s of S o l y o m : n a m e l y that
the m a g n e t i c m o m e n t has an oscillating z c o m p o -
n e n t a n d an ellipsoidal spiral c o m p o n e n t in the
x - y plane.
References
[1] G. Will, B. C. Frazer, G. Shirane, D. E. Cox and P. J.
Brown, Phys. Rev. 140 (1965)A2139.
[2] J. Solyom, Physica 32 (1966) 1243.
[3] M. Lecomte, J. de Gunzbourg, M. Teyrol, A. Miedan-.Gros
and Y. Allain, Solid State Commun. 10 (1972) 235.