Chemical Physics 129 (1989) 483-489

North-Holland, Amsterdam
TEMPERATURE-DEPENDENT LUMINESCENCE SPECTRA
AND LIFETIME MEASUREMENTS
OF OCTAHEDRAL Se(W) AND Te(IV) HEXAHALOGENO COORDINATION COMPOUNDS
Joachim DEGEN and Hans-Herbert SCHMIDTKE
Institut fir Theoretische Chemie der Universitdt DiisseldorJ Universithtsstrasse I, D-4000 Diisseldorf 1, FRG
Received 1 August 1988
Emission spectra and lifetime measurements of microcrystalline A,SeC16, A= Cs, Rb and Cs2TeX6, X = Cl, Br excited in the
lowest electronic transition are reported for the temperature interval from T= 1.9 to 240 K. The results are explained by a model
which considers spin-orbit coupling, electron-electron interaction and the electron-phonon coupling (Jahn-Teller effect) of the
complex molecule MX:- . Evaluation of the measured data indicates that the lowest excited states F, and F4 resulting from the sp
electron configuration differ by only about 110 and 95 cm- for the Se(W) and Te(IV) compounds, respectively. For the
SeCla- complex, emission only from F, is observed at temperatures below 2.1 K. The emission properties of octahedrally coor-
dinated sz ions can be explained by simple models including kinetic aspects. The relative orders of magnitude calculated for the
decay rates correspond to predictions obtained from selection rules.
1. Introduction
The luminescence of s2 systems has been studied in
great detail for various ions of different valences
doped in various host crystals. In an extensive review
Ranfagni et al. [ 1 ] report experimental results and
theoretical models on the study of optical properties
of Tl+-like impurities in alkali halide crystals. The
problem of emitting s2 impurities is rather complex;
Fukuda [ 21 introduced four classes of chromophores
which are classified according to their emission be-
haviour upon A-band excitation (absorption band of
lowest energy). The compounds studied in this work
belong to group two of Fukudas classification (one
emission band, at least two decay constants) and, in
contrast to most monovalent s2 ions, exhibit at least
at He temperatures a resolved tine structure which
can be assigned to a progression in the tg mode of the
MX6 octahedron [ 3-51.
In this study the temperature-dependent lumines-
cence properties of some octahedral complexes with
central ion s2 configuration are investigated. Tem-
perature-dependent decay times can be explained us-
ing a three-level system. Several transition rates as
well as the energy gap between the lowest exited states
are calculated from the rate equations by comparison
with the experiments.
If the valence electrons are assumed to be localized
on the central ion, linear phonon coupling of tg vibra-
tions to electronic states can describe the lumines-
cence properties of Se (IV) and Te (IV) complexes
sufficiently well, the other coupling constants for al
and z2 vibrations being negligibly small.
2. Experimental
Microcrystalline powder samples of Cs2MX6
(M = Se, Te; X = Cl, Br ) and Rb,SeCl, were obtained
as described in the literature [ 61.
Some milligrams of the powder were brought on
the sample holder of an LT-3- 11 OC flow cryostat (Air
Products) for measurements at temperatures higher
than 4.2 K, for temperatures down to 1.9 K a bath
cryostat (Cryovac) has been used. Temperatures were
measured with a platinum resistor installed at the end
of the cooling linger of the flow cryostat and a carbon
resistor in case of the bath cryostat, in both instances
using electric temperature controllers. Measure-
ments were carried out applying various intensities
0301-0104/89/$03.50 0 Elsevier Science Publishers B.V.
(North-Holland Physics Publishing Division )
484 J. Deger, H.-H. Schmidtke /Luminescence spectra of Se(IV) and Te(IV) hexahalogeno complexes
of incident light in order to check the influence of
sample heating.
All emission spectra were obtained by excitation
with the 454.5 nm line of an Ar+ laser 165 (Spectra
Physics). For lifetime measurements the laser light
was pulsed by a mechanical chopper (pulse width < 1
ps) for lifetimes > 10 ns. For shorter decay times a
flashlamp 199F (Edinburgh Instr. ) with pulse width
< 10 ns tilled with nitrogen (A,,, = 337 nm) was used.
The luminescence was focused onto the entrance slit
of a 0.5 m double monochromator (GCA Mc-
Pherson) and detected by a thermoelectrically cooled
photomultiplier C3 1034 (RCA). Luminescence
spectra were recorded with standard photon count-
ing technique, for lifetimes 2 10 ps in multichannel
scaling with a ND66B multichannel analyzer and
,< 10 us applying time correlated single photon
counting using a time-to-pulse height converter 457
(EG&G). Results were stored and analyzed in a
minicomputer, and the emission spectra were cor-
rected for spectral response of the experimental setup;
lifetimes are obtained via a linear regression, the cor-
relation coefficient r2 for each decay constant being
at least 0.99 for a minimum of 10 analyzed channels.
3. Potential energy surfaces
Considering the s2 ground state and sp excited state
electron configuration of the free ion which are sub-
ject to an octahedral charge distribution in the envi-
ronment (quasi molecule approximation [ 1 ] ), one
obtains the I, ( A,,) level for the electronic ground
state and F, ( 3T,,) and F,( 3T,,) levels for the lowest
excited states (resulting from the 3P, and 3P, multi-
plets of the free ion) when electron repulsion and
spin-orbit interaction are taken into account [ 11. The
vibronic coupling matrix for the excited sp configu-
ration up to first order has been calculated earlier [ 2 1.
The F, and F4 excited states are also coupled by eg
and 72g modes to higher excited states. However, F,
and I4 are not mixed by vibronic coupling (up to first
order) since there is no molecular normal mode of
symmetry ~~~ in the point group 0, necessary for this
intermixture. The energy hypersurfaces are obtained
from a diagonalization of the electron-phonon inter-
action matrix which includes spin-orbit coupling,
electron repulsion and potential energies f m,o3 Qf
o= 1) . ..) 6) being due to restoring forces with respect
to normal coordinates Q, with m, as the reduced mass
of mode j and o, the corresponding angular fre-
quency [2,3]. The five parameters (G for the elec-
tron repulsion, i for spin-orbit coupling and a, b and
c for vibronic coupling to aI,, eg and r28 modes, re-
spectively) may give rise to hypersurfaces of rather
different topology when applicable to various chro-
mophores. Parameter values G and [ are obtained,
e.g. from their absorption spectra [ 61. Two of these
vibronic coupling constants will vanish within the
simplified model.
Assuming the s and p electron to be localized on
the central ion of the octahedrally coordinated com-
plex, the operator aP/aQ, for the electron-phonon
coupling can be calculated in terms of spherical har-
monics Y,K( 0, 0) [ 7 J. Matrix elements of this oper-
ator which supply the coupling constants a, b and c
are obtained from evaluating integrals over angular
and radial parts of wavefunctions belonging to levels
resulting from the sp configuration. When the cou-
pling constant
w1 ~=~~mwwwIh
( !?(sp) ) is formulated in terms of integrals over
spherical harmonics Y;2 (@, 0) in which p(sp) is a
wavefunction of an sp level and a V/aQ, is the deriv-
ative of the electron-phonon coupling with respect to
the totally symmetric normal coordinate Q, of the
octahedron [ 5 ] all integrals over angular coordinates
( Y; 1 Y,K 1 Y;? ) with 1, I = 1, 2 for s and p electrons
and 2 = ? 4 (cf. table 1 in ref. [ 71) will vanish due to
symmetry selection rules [ 8 1. Calculation of the cou-
pling constant c leads to nonzero contributions of dif-
ferent sign which do, however, cancel. Only e coupling
(calculation of coupling constant b) yields nonvan-
ishing terms for localized electrons when calculating
matrix elements of the linear electron-phonon cou-
pling operator within first-order perturbation theory.
A quite similar result is also obtained from a delocal-
ized model which uses MO LCAO theory: The exci-
tation of an electron from an a,g antibonding
molecular orbital resulting from the central metal s
orbital decreases all metal-ligand equilibrium dis-
tances by an equal amount, but when occupying the
more strongly antibonding T,, orbital which arises
from a metal p orbital two of the ligands in trans po-
sition will be pushed away, both effects together re-
sulting in an overall lengthening of equilibrium
distances for these two ligands. The process, there-
J. Deger, H.-H. Schmidtke /Luminescence spectra of Se(I V) and Te(lV) hexahalogeno complexes
485
fore, leads to a symmetry decrease to D4,, which start-
ing from Oh is primarily effected by a nuclear
vibration of es symmetry. Thus finite values of b and
almost vanishing coupling constants a and c are ex-
pected leading to a distortion of the hypersurface in
the tg subspace with minima at D_,,, point symmetry
for the nuclei.
We can conclude that the description of the energy
hypersurfaces of the chromophores can be described
by three parameters G, c and b. The parameter b can
be obtained from a Franck-Condon analysis of the
intensity distribution of the emission spectrum [ 3 1,
G and c from the absorption spectra [ 6 1.
4. Results and discussion of vibronic spectra
Emission spectra of Se and Te complexes show a
distinct progression in the molecular vibrational tg
mode of the electronic ground state; the assignment
to this type of vibration is strongly supported by data
obtained from Raman studies [ 91. In table 1 param-
eters and vibrational energy quanta are given for
complexes considered in this work. Fig. 1 shows the
potential hypersurface calculated from a typical pa-
rameter set given in table 1. The potential for the ex-
cited r, state has three equivalent tetragonal minima
in the Qz, Q3 ( eg) subspace whereas the I4 state has
two tetragonal minima about 100 cm- above the
corresponding minima of the r, hypersurface as can
be seen from fig. 2.
Strong spin-orbit coupling of r4 (T,,) and higher
r,( IT,,) leads to a shoulder in the higher part of the
potential plane instead forming a minimum.
Fig. 3 shows the low-temperature emission spectra
of C@eCl,. At T>2.2 K the maxima are shifted
about 100 cm- to higher energies compared to the
T= 1.9 K spectrum, the former being better resolved
than the latter. This feature can be explained from
the potential energy surfaces described above: Since
transitions from the lowest excited state are not al-
lowed (electric dipole forbidden, also when includ-
ing vibronic coupling up to first-order perturbation),
emission from I4 being electric dipole allowed dom-
inates the spectrum at temperatures above T= 2.2 K
due to thermal population of I4 from the r, below.
At lower temperature the transition intensity which
is the product of population and transition probabil-
ity decreases for emission from the upper level be-
cause of the lower thermal population. At about
T= 1.9 K the strongly forbidden emission from the
level l-r dominates the dipole-allowed emission from
the upper state. The shift of about 100 cm- of the
relative maxima (cf. fig. 3) corresponds to the ener-
getic separation of the I4 and I1 potential minima
calculated above, cf. fig. 1. The intensity distribution
of the emission band on the other hand shows only
minor changes cooling from T= 2.2 to 1.9 K indicat-
ing that the potential minima of both excited elec-
tronic states nearly remain at the same position in
the Q2, Q3 space which also is expected from the cal-
culation of the r, and r4 potential sheets, see figs. 1
Table 1
Peak maxima of A, B and C bands, electronic parameters G and c, vibronic coupling constants b and vibrational quanta of Se(IV) and
Te( IV) complexes. Energies in cm-i, coupling constants in 10m4 erg/cm; a hyphen denotes not observed
[TeBr612- [TeC16]*- [SeCl,]*- Remarks
A 21750 25200
B 26100 31150
C 30100 34800 39000
absorption bands
Y
3100
4350
3300
5950 2500 =
obtained from A, B, C [6]
b
uig
68
-4.5
.175 (-)
151 (145)
-4.5
288 (-)
245 (-)
-4.0
278 (-)
242 (240)
T x 6 coupling constant a)
vibrational quanta from
Raman (luminescence) data
a) Taken from ref. [ 31.
486 J. Deger, H.-H. Schmidtke / Luminescence spectra of Se(I V) and Te(I v) hexahalogeno comple.xes
Fig. 1. Potential hypersurfacesofT,(3T,,) and r,,(3T,,) levels in the Q2. Q, (6,) subspace for a=c=O, b=4x IO- erg/cm, G=[=0.3
eV.
and 2. The fact that the spectrum is less resolved at
lower temperature may be due to the superposition
of emission from both excited states, emission from
the upper state not being completely quenched. Since
virtually the same results are obtained for the
Rb,SeCl, system, the temperature-dependent shift of
the emission spectrum cannot be explained by the
presence of a phase transition. In addition, support
for the assignment of the spectra in fig. 3 can be ob-
tained from temperature-dependent lifetime mea-
surements which will be described in section 5. For
the Te (IV) complexes no shift of the emission spec-
trum could be detected.
5. Kinetics within a three-level system and lifetime
measurements
The temperature-dependent lifetime measure-
ments can be explained by a three-level system, cf.
fig. 4, representing the electronic ground state
l-r (A,,) and the two lowest excited states, I, ( 3T,,)
and I-,( 3T,,). After excitation into the A band (ab-
cs,seci,
--T=,OK
-4; 2K
A.,,~%~
2-
Fig. 2. Projection of hypersurface as in fig. 1 taken at Q2 =
J7Q3.
Fig. 3. Low-temperature emission spectra of Cs,SeCl, at T= 10
K (dashed line) and T=1.9 K (solid line): A,,,=454 nm (A
band).
J. Deger, H.-H. Schmidtke / Luminescence spectra of Se(I V) and Te(I V) hexahalogeno complexes 487
nL f
, i
:,, : k_ rL(3u
k+;, I:,
:
I ;
k,
~
I - , (3T,J
- allowed
I \
1 4
YY
,
I )
- wbronlc
,
I
I 1
_-+ forbidden at least up to farst
--a order perturb&on theory
QA, , )
Fig. 4. Energy levels of the lowest sp terms r, and r4 resulting
from T,, and r, (A,,) ground state from s2 configuration. Ra-
diative (-+ ) and nonradiative ( * ) rates used in the kinetics of
a three-level system are also indicated.
sorption band of lowest energy) the two excited states
are assumed to be thermally populated within several
nanoseconds, i.e. nonradiative processes lead to a
Boltzmann distribution for the population of the vi-
bronic manifold of the sp levels before relaxation to
the electronic ground state becomes important. Two
rate equations will describe the relaxation of the
chromophores [ 10 ] (see fig. 4):
ri,=-(k,+k_)n,+k+n,,
&=k_12,-(kk4+k+)&.
(1)
They can be simplified by applying the following
symmetry arguments:
(i) The radiative component of the rate constant
k,corresponds to an electric-dipole-forbidden transi-
tion which for the molecule is also forbidden by lin-
ear electron-phonon coupling since an octahedron
cannot supply normal vibrations of symmetry zig
which are necessary for making the l7, ( 3T,,)
+T, ( A,,) transition vibronically allowed: similarly
the corresponding nonradiative transition is also for-
bidden due to the lack of an a,, vibration of the
octahedron.
(ii) The Arrhenius formula k_ =3k+ exp( -AEI
kT) with k as Boltzmann constant and AE denoting
the energy gap between the excited levels F4 and rl
represents as in (i) a forbidden transition due to
lacking normal modes of z,, symmetry. The factor of
three results from the statistical weight of the three-
fold degenerate r4 state.
(iii) The rate k4 refers to an electric-dipole-al-
lowed radiative and a vibronically allowed nonradia-
tive transition.
Thus a relation k4 a k,, k,, k_ can be assumed. In
the literature, however, also k, x==k4 has been used
when treating the kinetics of other s2 systems [ 1 l-
13 1, as well as AE < kT which is only valid for low
temperatures, cf. table 2 (see the discussion below).
Solutions nj( t), j= 1, 4 of the rate equations ( 1)
are bi-exponential functions of time,
j=l,4,
(2)
with a,, and az4 being constants which are deter-
mined by boundary conditions. r, j= 1,2 are the roots
of the coefficient matrix given by eq. ( 1 ),
q-:=f(k,+k_+k,+k+)
Ti[(kl+k_-kq-k+)2+4k+k_]12.
(3)
A b&exponential decay curve for the emission from
I4 is expected; the decay constant rZ is dominated by
the rate k4, cf. table 2.
From the solutions of the rate equations ( 1) and
by inspection of fig. 4 one arrives at the following
results:
(a) For kT< LI E, when r4 is not thermally popu-
lated from I,, the decay curve has a single exponen-
tial decay form. For T-+0 the rate constant k, will be
obtained from the decay constant 7,;
(b) there is a temperature region where k_ domi-
nates the depopulation of r,: from an Arrhenius plot
of In ( 1 /71 ) versus 1 /T, parameter values for k_ and
AE are obtained. In fig. 5 an Arrhenius plot of the
decay constant pi is given for CszTeBr6 and table 2
shows the corresponding kinetic constants calculated
for all complexes studied. Three temperature regions
can be distinguished:
(I) Below about T= 18 K (for Se(IV) 30 K) r is
nearly independent of temperature, fitting r1 to a for-
mula 1 / 71 = kl exp ( - AE, /kT) supplies the parame-
ters k, and AE, which are given in table 2. For a
physical explanation of AE, see below.
(II) In the region up to about T= 200 K (for
Se( IV) only about 45 K) the luminescence intensity
is approximately constant, r, decreases more rapidly
with increasing temperature than in region I and
k_ =3k+exp( -AE/kT) dominates the decay
constant.
488
Table 2
J. Deger, H.-H. Schmidtke /Luminescence spectra qf Se(W) and Te(I V) hexahalogeno complexes
Experimental results obtained from temperature-dependent lifetime measurements and low-temperature emission spectra of Se (IV) and
Te(IV) complexes. For notations see figs. 4 and 5
[SeC16]*- [TeBr6]- [TeCl,]-
region I r-(T-0) (s-l)
k, (s-l)
AE, (cm-)
region II k, (s- I )
3k+ (SC)
AE (cm-)
region III k, (SK)
AE3 (locm-)
50
5x104
12(2)
lo9
1.3x lo6
llO(10)
-b)
-bJ
330 (450) a 200
3x10) 103
14(4) lo(9)
~10~(1.9X106)a) x 1oy
1.2x106 8.3x lo5
96(3) 95(3)
2x 10
1.3(2)
4x 100
1.7(2)
*) From ref. [ 91, cf. text. I Not observed.
(III) In this region the luminescence intensity as
well as the decay constant decreases rapidly with in-
creasing temperature, i.e. nonradiative rates k~,,, (j= 1,
4) are the main contributions to the luminescence
decay. The temperature dependences of the k,,,, are,
however, not considered in the rate equations ( 1 ),
cf. the three-level system in fig. 4. The temperature-
dependent decay constants will be discussed for the
regions I-III separately.
Region I. For T-+0 only one decay constant is ob-
served. A mono-exponential decay is expected since
luminescence occurs from the lowest excited state l-r
only. For higher temperatures in region I the lumi-
nescence decay curve becomes bi-exponential. Since
c
i
Fig. 5. Temperature dependence of the slow decay constant T, of
CszTeC16 on A-band excitation (A,,,=454 nm).
luminescence from r4 now dominates the emission
this level is depopulated by two decay channels. The
temperature dependence of T is supplied by k, which
describes the radiative as well as nonradiative tran-
sitions from the lowest excited I, to the ground state
I-,: k, is strictly forbidden within the model em-
ployed. This is supported by k, values of about lo3
s- compared to rates of 1 O9 s- obtained for allowed
transitions. The parameter k, and its temperature de-
pendence can be explained by a more detailed theo-
retical model which includes intermolecular modes
of proper symmetry, e.g., a crystalline rslg mode. For
Bi3+ in cubic host crystals a zig promoting mode has
been reported which is assigned to a rotational vibra-
tion of the complex octahedron relative to the envi-
ronment making the transition r, (T,,) +I, ( A,,)
vibronically allowed [ 12,141.
The energy parameter AE, obtained by fitting the
temperature dependence of the slow decay compo-
nent may also be explained by a more complicated
model which assumes for the system Ga+ doped in
KBr a small splitting (several cm- ) of I4 due to
mixed quadratic terms of the vibronic coupling op-
erator [ 15 1. Corresponding splittings calculated for
Se(IV)andTe(IV)complexesare 12to 16cm- (cf.
table 2 ).
Region II. In this temperature region k_ (see
above) is the dominant temperature-dependent tran-
sition rate, the total intensity being nearly constant.
The AE values obtained from the Arrhenius plots are
given in table 2, the splitting of 1 lo? 10 cm- in the
case of [SeC16]*- agrees well with the shift of 105
J. Deger, H.-H. Schmidtke /Luminescence spectra of Se(I V) and Te(I V) hexahalogeno complexes 489
cm- observed from the emission spectrum at 1.9 and
2.2 K supporting the proposed assignment. The larger
error compared to the other compounds studied is due
to the fact that region II extends only from about
T= 30 to 45 K, whereas for the other compounds this
region is much larger (from less than 25 K to nearly
200 K), allowing to carry out a better fitting.
The relation k4 x- k,, k,, k_ as mentioned above
holds with k, taken from region I, k+, k_ determined
from the Arrhenius plot and k4 from the short-decay
constant TV. The relative order of magnitude for these
rates can be estimated from simple selection rules: k4
is electric dipole allowed, k, and k_ are forbidden
up to first order in vibronic coupling in the molecular
approximation. Setting k, B k4 as assumed in earlier
treatments of the kinetics between three level sys-
tems may lead to different assignments [ 1 l-l 31.
Blasse et al. [ 111, for example, studied temperature-
dependent lifetimes of [TeBr,] 2-; they report for the
region II AL? values of 90 cm- and for region I k, of
450 s-l which are in fair agreement with the results
given in table 2. But the rate k4 ( 1 /r2 in the notation
of Blasse et al. [ 111) of 1.9 x 1 O6 s- differs from ours
by three orders of magnitude. This discrepancy may
result from assuming k, zs- k4 and in addition
AE << kT as inferred from ref. [ 10 1. Two decay con-
stants in the milli- and nanosecond range have been
observed for a lot of s2 systems such as Tl+ in alkali
halides [ 21, Bi3+ in CaO [ 121 or in SrS [ 141 and
Pb+inSrQ [13].
Region III. At higher temperatures the decay
mechanism is dominated by nonradiative transitions
quenching the luminescence. Corresponding param-
eters for this temperature region are also given in ta-
ble 2. Quenching mechanisms for [ TeX6] 2- (X = Br,
Cl) have been recently studied also by Blasse et al.
151.
6. Conclusions
The temperature-dependent decay curves of
Cs,MX,, M = Te, X = Cl, Br and Rb2SeC16 were mea-
sured to be bi-exponential as was found in s2 systems
investigated earlier. The results can be explained by
a three-level system from which rate constants are
determined as well as the energy gap between the two
excited states. For the [ SeC16]2- compounds the
emission pattern exhibits distinct line structure aris-
ing from vibronic coupling to eg modes the spectrum
moving to lower energy at 1.9 K due to the
I-, ( 3T,,) +I, (A,,) transition which is subject to a
second-order dynamic Jahn-Teller effect in the ex-
cited state. The presence of a single progression is ex-
plained by a model which predicts only the vibronic
coupling constant b to be different from zero. The re-
sults demonstrate that time-resolved temperature-
dependent emission spectroscopy, already earlier ap-
plied on ionic s2 systems, is an important tool for
characterizing also lower excited states of coordina-
tion compounds containing the same central metal
electron configuration.
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