Pergamon

SINGLE CRYSTAL MAGNETIC SUSCEPTIBILITY OF THE QUASI-ONE-DIMENSIONAL

ANTIFERROMAGNET KFe!$
Satish K Tiwary and S. Vasudevan*
Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore, India
(Received 22 August 1996 by C.N.R. Rao)

The single crystal magnetic susceptibility of the quasi-one-dimensional

antiferromagnet KFe$ is reported. The high temperature isotropic sus-
ceptibility is typical of a spin-l/2 Heisenberg chain. The intra- and inter-
chain exchange constants are -44.7 K and 53.94 K, respectively. At 250 K,
KFeSZ exhibits a well defmed transition to a three-dimensionally ordered
antiferromagnetic state. The calculated perpendicular susceptibility at 0 K
considering the zero point reduction in magnetisation for a S = l/2 one-
dimensional chain from spin wave theory is close to the projected value
obtained from the experimental data. Copyright 6 1997 Elsevier Science
Ltd

Keywords: A. magnetically ordered materials, D. exchange and

superexchange.

1. INTRODUCTION reveal any anomaly at T = 250K. The reports on the

temperature dependence of magnetic susceptibility by
KFe$, a linear chain insulating antiferromagnet and
different investigators are conflicting, and so are the
one of the earliest reported ternary alkali metal thio-
reported values of the effective magnetic moment, peff,
ferrates [l] has been widely studied both as a model one-
which ranges from 0.8~~ [14] to 4.6~~ [3]. The mag-
dimensional magnetic system and as a spin analog of
netic data reported so far have been on powder samples.
the iron-sulfur ferrodoxin proteins. These proteins and
There has been no report on the single crystal suscepti-
KFe& share a common structural motif - chains of edge
bility of K.Fe$. A major source of error and the possible
sharing [FeSJ tetrahedra. KFeSZ crystallizes in CUc
origin of the discrepancies in the powder susceptibility
monoclinic space group with the [Fe!&],, chains sepa-
measurements is the formulation of ferromagnetic
rated by potassium atoms (Fig. 1). The interchain Fe-Fe
oxide impurities [14]. It is known that on exposure to
distance (6.6 A) is much larger than the intrachain Fe-Fe
air KFeSZ is slowly oxidized to KFe02, a high spin Fe3+
distance (2.7 A) and so, magnetically, the compound has
ferromagnet (T, = 960 K) [19] which could mask the
a pronounced one-dimensional character [2].
true magnetic behaviour. Thus, in spite of numerous
Extensive Fes7 Miissbauer [3-lo], neutron diffrac-
studies, the nature of the spin state and magnetic behav-
tion [ll-131, magnetic susceptibility [2, 12-151 and
iour of KFeSZ still remains unclear. It is with this in mind
optical spectroscopic measurements [16-181 on IWe&
that we have carried out a detailed study of single crystal
have been reported. The results and their interpre-
magnetic susceptibility of KFe&.
tation, however, differ greatly from author to author.
Neutron diffraction studies have shown that below
2. EXPERIMENTAL
TN = 250 K, the Fe3’ spins are antiferromagnetically
coupled along the chain and form ferromagnetic sheets KFeSZ was prepared by heating a 4 : 1 molar mixture
in the ab plane. Magnetic susceptibility studies, how- of K2C03 and oxide-free iron powder in a stream of
ever, with the exception of one [14], have failed to dry H2S at 1000 K for 24 h. The product was cooled to
ambient temperature over a period of 24 h, and then
extracted with cold water. This procedure gave fine
* To whom all correspondence should be addressed. permanganate-colored, needle-shaped crystals typically

449
450 SINGLE CRYSTAL MAGNETIC SUSCEPTIBILITY OF ANTIFERROMAGNET KFe!$ Vol. 101, No. 6
5-1Omm in length and 0.5-l mm width. The needle
axis is the c-axis. The crystals were again heated in
flowing H# at 773 K for 12 h. Under these conditions,
KFeOz is known to convert to KFe$ [14, 191. Care was
taken not to expose the crystals to air or moisture after
the H$S treatment.
Magnetic susceptibility measurements in the tem-
perature range 45-300K were made on a Faraday
magnetic balance. A large number of needle-like crystals
were aligned parallel onto a thin quartz plate using
silicone grease. The plate was then suspended from the
balance by an arrangement similar to that reported in
[20]. For the high temperature measurements, the crys-
tals were tightly packed and sealed under vacuum in
small thin-walled quartz ampoules. Calibration with
HgCo(NCS)4 was repeated under identical conditions.
The susceptibilities reported are for two directions. In the
temperature range 250-800K with the applied field
parallel and perpendicular to the c-axis, which is also
the needle axis of the crystal, while for temperatures
below 25OK, the field is parallel and perpendicular to
the magnetisation axis. The magnetisation axis is known
from neutron diffraction studies [ll] to be at an angle
of 13” to the chain axis.
3. RESULTS
The temperature variation of the magnetic suscepti-
bility of KFe$ crystals is shown in Fig. 2. The diamag-
netic as well as the van Vleck paramagnetic contribution
have been subtracted from the data. The latter was
evaluated from the EPR g value of 2.025 [21] and the
energies of the optical transitions; its value is
9 x 10e7 emu mol-’ . The susceptibility of KFe& is typi-
cal of a low-dimensional antiferromagnet undergoing
a three-dimensional transition. The Neel temperature
is 250 K. In Fig. 2, the data above 250 K is the suscepti-
bility parallel and perpendicular to the c-axis and is
b
l K+ l F&O s2-
Fig. 1. C 2/c crystallographic structure of KFe$.
The lattice parameters are (a = 7.082, b = 11.329,
c = 5.403, p = 113.2).
3.0 ,
2002
0.0 200.0 400.0 600.0 6C .O
Temperature(K)
Fig. 2. The experimental magnetic susceptibility of
KFe$. Above 250 K, the external field is applied parallel
and perpendicular to the c-axis. Below 25OK, the field
is parallel and perpendicular to the magnetisation axis.
isotropic within the experimental limits. The high tem-
perature isotropic susceptibility shows a broad maximum
at 565 K (T,, = 565 K, xmax= 2.7 x 10e4 emu mol-‘),
and even at the highest temperature, does not show
Curie-Weiss behaviour. The low temperature
(T c 250 K) behaviour is typical of antiferromagnetic
ordering where the susceptibility parallel to the mag-
netisation axis shows a sharp decrease below TN whereas
the perpendicular susceptibility shows only a weak
temperature dependence. The extrapolated value of
the perpendicular susceptibility (xl) of KFeSz at
0 K comes out to be 2.7 x low4 emu mol-‘. The present
single crystal susceptibility value of 2.3 x
10m4emu mol-’ at 300 K is much lower than the pre-
viously reported powder susceptibility values, confirm-
ing substantial impurity contribution in the powder
susceptibility data.
4. DISCUSSION
The broad maximum at 565 K and the non Curie-
Weiss behaviour in the susceptibility of KFe$ are due
to the short range spin correlations which manifest
at temperatures much above TN in low-dimensional
systems. The TN is, of course, due to interchain inter-
actions which lead to three-dimensional ordering
below 250K. The low value of magnetic susceptibility
and its isotropic behaviour above TN suggest that
KFeSz may be modelled as an spin-$ one-dimensional
Heisenberg chain. Support for an S = l/2 model
comes from the experimental value of the quantity
xmaxT,,/g2. This quantity is an handy criterion for
determining the spin state appropriate for the one-
dimensional chain compound under investigation [22].
Vol. 101, No. 6 SINGLE CRYSTAL MAGNETIC SUSCEPTIBILITY OF ANTIFERROMAGNET KFeSz 451
For a one-dimensional Heisenberg chain the values of
this quantity for various spin states are 0.0353 for
S = l/2; 0.089 for S = 1; 0.16 for S = 312; 0.25 for
S = 2; and 0.38 for S = 512 [22]. From the experimental
susceptibility data and EPR determined g = 2.025 [21]
of KFeS*, the value of xmaxTmax/g2 is 0.0375 which is
closest to the value for a S = l/2 chain.
We have evaluated the exchange constants: J,
the intra-chain nearest-neighbour exchange, and J”, the
interchain exchange using the properties of a spin-$
antiferromagnet Heisenberg chain. According to Bonner
and Fisher [22, 231, for a spin+ chain of in8nite length,
kB T,,
- = 1.282. (1)
IJI
Substituting the experimental value of Tmax = 565’K, in
equation (l), we arrive at a ]J ) value of 440.7 K. The
interchain exchange, J’, was calculated from TN using
a relationship originally due to Oguchi, who had calcu-
lated the ratio of the exchange parameters, J/J’, from TN
by a Green’s function technique [24],
4qs + 1)
kB TN
(2)
/J/= 3IJI.l’ . 1. Bronger, W., Angew. Chem. fnt. Ed., 20,1981,52.
The integral ZJMf has been numerically evaluated.
Substituting the values of TN, IJ I, and S in equation (3),
the value of the integral ZJIJf comes out to be 1.8, and
]J’] = 53.94 K.
Using these values of J and J’, the perpendicular
susceptibility at OK, xl(O), was calculated using non-
interacting spin-wave theory [25], and compared wi.th the
experimental value. In spin wave theory, the perpendi-
cular susceptibility at absolute zero is given by
0 Taft, C.A., Solid State Commun., 38, 1981, 205.
x’Ko=(1~~,2) rnss
l-M,, 3 (3)
1 [
where x”, is the perpendicular susceptibility as given by
the mean field approximation; (Y,the anisotropy factor, is
g&& /2Sz I J I, which for the present one-dimensional
system is 0.0612. M,o is the fully aligned sublattice
magnetisation and AMso is the zero point deviation
from the completely aligned state and is independent of
temperature. x”, , the mean field perpendicular suscept-
ibility, is, for J = 440.7K and J’ = 53.94K,
4.11 x 10v4 emu mol-‘.
According to the spin wave theory, the zero point
deviation in magnetisation, Ai%f,s/&f~o,
for a spin+ linear
Heisenberg system is
(4)
which, for (Y= 0.0612 and S = $ is 0.3304. Substituting
the values of x “,, a, and AMsBIM,, in equation (4) we get
xl(O) = 2.75 x lop4 emu mol-‘. This value may be
compared with the extrapolated experimental value of
2.7 x 10e4 emu mol-‘.
In conclusion, the present single crystal magnetic
susceptibility measurements on the linear chain anti-
ferromagnet KFeS2 indicate an S = $ ground state for
the Fe3+ ion and a temperature dependence typical of
a one-dimensional system. Three-dimensional antiferro-
magnetic ordering sets in below TN = 250K. The inter-
and intra-chain exchange constants are -440.7K and
53.94 K, respectively. Support for an S = f model comes
from the fact that the calculated perpendicular suscepti-
bility at OK (2.75 x 10m4emumol-‘) evaluated con-
sidering the zero point reduction from the spin wave
theory is quite close to the projected value obtained
from the experimental data (2.7 x 10e4 emu mol-‘).
The low value of susceptibility in KFeS2 is adequately
explained by quantum spin reduction for an S = 1 chain.
Acknowledgement-The first author thanks CSIR, New
Delhi, India for a research fellowship.
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