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Solid State Communications, Vol. 5,pp. 267-270, 1967.

Pergamon Press Ltd. Printed in Great Britain

2~IN PARAMAGNETIC FAYALITE (Fe

MOSSBAUER STUDIES OF Fe

3SiO4)~

M. Eibschiitz and U. Ganielt


The Weizmann Institute of Science, Rehovoth, Israel
(Received 13 February 1967 by E. Burstein)

Mssbauer absorption spectra in Fe3SiO4 were taken


over the temperature range 80 - 1000K. The quadrupole splitting of the absorption line as a function of
temperature was measured. The results show, that 2~
ionselectric
has different
values, corresponding
to the
the
field gradient
tensor at the sites
of two
the sites
Fe
of different point symmetry which are known from x-ray
data.

of gravity of the corresponding peaks. Some


typical unretouched Spectra are reproduced in

AS PART of a series of investigations on divalent


iron compounds, being carried out in our laboratones, we studied Fayalite (Fe
2SiO4) by means
of the Mssbauer effect.

Fig. 1.
Instead of the two peaks of equal intensity,
which are usually observed when the ferrous ion
occupies a site of distorted octahedral symmetry,
we found in the present case that one of the lines
had split into two, this secondary becoming more
pronounced at high temperatures. This rather
interesting feature is easily explained by the
crystallographic data. Fe2SIO4 belongs to the
space group ~nma (D ~~6h), having four molecules
per unit cell. ~
The ferrous ions occupy two
non-equivalent positions, of which there
2~ion are
is four
surrounded
of each typeby
pera distorted
unit cell. octahedron
Each Fe of oxygen
ions. The point symmetry at the site of the Fe~
ion has only a center of symmetry (T) at one
position and a mirror plane (m) at the other. 8
The different point symmetries at the two sites
give rise to different values for the components
of the electric field gradient (EFG) at these sites
and hence - to different quadrupole splittings
(Q. S) of the upper M~ssbauerlevel of the Fe
nucleus. This in turn explains the secondary
splitting of the Mc~issbauerpeak. The results of
the quadrupole splitting at both sites as a function
of temperature are shown in Fig. 2.

Fe3SiO4 was prepared by mixing Fe203,


Si02 and Fe in stoichiometric proportions. The
mixture was sealed in an evacuated silica tube
and placed in a 1000C furnace for a period of
24 hr. The resulting compound was checked by
x-ray photographs to check that it was a single
phase material,
The MO~ssbauerspectra were obtained by
means of a constant velocity automatic recordin
improved version
a cryofurnace
describinganspectrometer.
1 Theofabsorber
was contained
ed by Sharon and Treves2, and spectra were
taken covering a temperature range between 80
and l000K. The source was ~Co In Pd. ~ The
spectra were recorded directly on an x-y
recorder and the quadrupole splittings were
determined from the distance between the centers
_________________________________________

The research reported in this document has


been sponsored in part by the Air Force Materials Laboratory Research and ieclinology
Division AFSC through the European Office of
Aerospace Research, United States Air Force
Contract F 61052-67-C-0040.
t Part of a Ph. D. thesis to be submitted by U.
Ganiel to the Feinberg Graduate School of the
Weizmann Institute of Science,
*

At low temperatures we found (to within


the experimental resolution) the same value for
the Q.5. at the two sites, namely (3.05 0.03)
267

2~

Vol.5, No. 4

MOSSBAUER STUDIES OF Fe

268

Sourc* Co57 in Pd

Absorber ~
~

Si 04

the spin orbit interaction can lead to even


further splitting. For each such atomic level,
the EFG tensor
can beThe
calculated
I! thesplitting,
eigenfunctions
are known.
quadrupole

T= 296 ~

in the case of Fe (I

3/2) is given by

e2 q Q

~ 2/~

)%

where q = V,,, Q is the quadrupole moment of


the I = 3/2 nuclear level and

T= 387 ~K

T~639K

,.._.

vV
xx

\I
yyJI
/

/
V

zz

Since the electronic relaxation times are

-s

T= 759 K

-4

-2I

0I

Veloct Y 1mm.
i
Se

expected to be much smaller than


h / ~ EQ
(~3.10_B sec), the actual value of ~EQ which
the nucleus feels become a thermal average
of the values of ~ EQ in the different states. At
low temperatures only the lowest atomic levels
contribute to this average so that ~EQ normally
approaches some saturation value, which, for
Fe2~ compounds, is typically around 3 mm/sec.7
It is only at higher temperatures, that the higher
levels become more important and thus the
details of the crystal field influence on the Q. S.
of the Mssbauer lines become important. In
the case of Fe
2SIO4, the existence 2~ions
of two differmeans
that
there
are
different
crystal
fields
ent types of lattice sites for the Fe at those
sites, a situation
which
manifests itself more
pronouncedly
at high
temperatures.

FIG. 1
In cases where the point symmetry at the
Mssbauer spectra of Fe
2 Si04 at
Pd. Counting
time
was
different5~in
temperatures.
The
source
wassec.
30
Co per channel for the first two
spectra and 100 sec for the other two,
mm/sec at 80K. This is about the characteristic value for the Q. S. in compounds of Fe2 + ~
at low temperatures, in a distorted octahedral
environment. At higher temperatures, on the
other hand, the secondary splitting became more
pronounced, giving at 1000K the values:
(1. 56 0. 06) mm/sec for one site and
(1.40 0. 06) mm/sec for the other. These
facts can be understood if we consider the EFG
at the site of the Fe2~ion. The most important
contribution to the EFG comes from the electronic d-shell, which has the configuration d6.
In an octahedral field, this leads to a lower
triplet T
21, and an upper orbital doublet, E,.
Deviations
split
the orbitally
from octahedral
degeneratesymmetry
levels further,
can then
and

nuclear site is higher than in Fe2SiO4, the con-.


ations
of crystal
field
parameters
from the
siderations
outlined
above
permit actual
calcultemperature dependence of the Q. s, ~~ In the
present case however, the point symmetry at
both sites is so low, that any calculation of this
type would require a large number of parameters.
To attempt such a calculation, it is necessary
that the experimental results be of high accuracy,
in order to get unambiguous results, On the
other hand, the secondary splitting described
above is relatively small, and thus the resolution is rather poor. This reduces the accuracy
considerably. Hence, determination of the
crystal field parameters via some curve fitting
procedure does not seem meaningful.
In an attempt to identify each of the secondary peaks with one of the two sites, we tried the
following procedure. We prepared the compound
2 ~ Ion substitutes
the been
Fe2 shown
ion in the
CaFeSiO4,
for whichfor
it has
~ site
~ the
Ca the mirror plane (m). The Mssbauer
with

2~

Vol.5, No.4

269

MOSSBAUER STUDIES OF Fe
I
301

S
0

25-

.5.

E
E

1
0

%
0

20-

~,
0

Oo

Absorber
~

Fe2 Si 0~

1.5-

00~

Oo

9.

1.0

~0
0

0.5
00

200

400

600

800

000

Temperature [KJ

FIG. 2

Quadrupole splitting as a function of temperature for Fe


2SiO4 - Full circle and open
circles give the experimental values for the
two different iron sites.

spectrum of this compound consisted of two lines


without the secondary splitting observed in
Fe2SiO4, which means that all the ferrous Ions
occupy equivalent sites. The Q. S., however,
turned out to be considerably smaller than in
Fe2SiO4, namely: (2. 18 0. 03) mm/sec at
room temperature and (1.21 0. 03) mm/sec at
880K. Thus the EFG in CaFeSiO4 is 2~
not in
the
same as in either of the two sites of Fe
Fe2SiO
4, and hence this method did not give us
the identification we had hoped for.

Since Fe2SiO4 undergoes a transition and


becomes antiferromagnetic below 65K 10, it is
possible that further investigations at lower
temperatures could help to clarify the situation
further. ~
We would like to thank Prof. S. Shtrikman
for suggesting this study and for his constant
interest.

References
1.

M5ssbauer Effect Spectrometer, produced by Elron, Electronic Industries, Haifa, Israel.

2.

SHARON B. and TREVES D., Rev. Sci. Instr. 37, 1252 (1966).

3.

Purchased from New England Nuclear Corporation, U.S.A.

4.

HANKE K., Neues Jb. Miner. Mh. 8, 192 (1963).

5.

International Tables for x-ray Crystallography, Vol.!, Kynoch Press, Birmingham (1952).

6.

See e.g. INGALLSR., Phys. Rev. 133, A787 (1964).

270

MOSSBAUER STUDIES OF Fe

Vol.5, No.4

7.

Strictly speaking, spin orbit effects and mixing of higher states into the ground state influence
the value of the E PG at low temperatures, but in most cases the general arguments described
above are still valid.
-

8.

EIBSCHUTZ M., GANIEL U. and SHTRIKMAN S., Phys. Rev. 151, 245 (1966).

9.

EIBSCHTZ M,, GANIEL U. and SHTRIKMAN S., Phys. Rev., (in press).

10. SAUTOROR.P., NEWNHAM R.E. and NOMURA S., J. Phys. Chem. Solids, 2?, 655 (1966).
11. NEWNUAM R. E., CARON L. G. and SAUTORO R. P., J. Amer. Cer. Soc. 49, 284 (1966).
12. KUNIG W., LINDQUIST R. H. and CONSTAVARIS G., reported in the 12th Annual Conference
on MagnetIsm and Magnetic Materials (1966).

Des spectres dabsorbtion Mdssbauer en Fe


2SiO4 ont
dt faites dans une range de temperature du 80 - I OOK.
On a mesur4 le couplage quadrupolaire de la raie d
absorbtlon fonction de la temperature. Les rdsultats
montrent que le tenseur gradient 2~a
du champ
dlectrique
des valeurs
differentes,
correspondant
symmetries de points
dans les positions
des ions aux
de Fe
diffdrents connus des donnes crystallographiques.