Journal of Electron Spectroscopy and Related Phenomena 86 (1997) 133–138

Magnetic operators for Ti 3+ and Cu 2+ ground states

Philippe Sainctavit
Laboratoire de Minéralogie–Cristallographie, CNRS URA9, F-75252 Paris Cedex 05, France

Abstract

We have checked the XMCD sum rules through an analytical calculation of Cu 2+ L 2,3 edges in octahedral symmetry. It is
found that XMCD sum rules are fully satisfied in the framework of the crystal field multiplet approach resulting from the very
general arguments developed in their derivations by B.T. Thole and collaborators. Analytical expressions for the orbital
magnetic moment hL zi, the spin magnetic moment hS zi and the magnetic dipole term hT zi are obtained as functions of crystal
field strength and spin–orbit couplings. The nullity of hT zi is specially examined through group theory considerations, and it is
found that at low temperature the hT zi contribution can be much larger than the hS zi contribution in the spin sum rule. The case
of Ti 3+ in octahedral symmetry is also considered and it is found that, even for no spin–orbit coupling, hT zi can be non-zero.
q 1997 Elsevier Science B.V.

Keywords: Multiplet; XAS; XMCD

1. Introduction In order to check the nullity of hT zi, we have per-

After the publication by Theo Thole et al. [1], Paolo
Carra et al. [2] and Massimo Altarelli [3] of the magnetic
sum rules applied to X-ray absorption spectra, numerous
papers have addressed the validity of these rules. In
some experimental papers, the orbital magnetic moment
hL zi and the spin magnetic moment hS zi have been
extracted from X-ray magnetic circular dichroism
(XMCD) measurements and compared with either
experimental data (neutron diffraction) or theoretical
calculations [4]. In other publications [5–7] a more the-
oretical check has been performed by the calculation of
the theoretical XMCD spectra and of average values of
hL zi, hS zi and the magnetic dipole term hT zi.1 One limita-
tion of the second sum rule concerns hT zi, which can be
non-zero even though it is often assumed to be zero for
the L 2,3 edges of transition metals.
1
Following Ref. [2], T z is the third component of the magnetic
dipole operator T = ∑i si − 3ri ·(si ·ri )=ri2 .
0368-2048/97/$17.00 q 1997 Elsevier Science B.V. All rights reserved
PII S 0 36 8- 2 04 8 (9 7 )0 0 05 8 -3
formed an analytical calculation of Cu 2+ L 2,3 absorp-
tion cross sections in octahedral crystal field
symmetry. This calculation was introduced by Theo
Thole and Gerrit van der Laan, who gave the intensi-
ties of the electric dipole transitions for 3d 9 in O 3
symmetry and discussed the case of D 4h and C 4h [8].
Despite the well known Jahn–Teller effect that Cu 2+
undergoes in most compounds, almost pure octahedral
Cu 2+ can be created by coordination chemistry.
Without making a complete calculation of Ti 3+ L 2,3
edges, we have used the series of codes developed
by Thole to obtain numerical expressions for the
expected values of the useful magnetic operators L z,
S z and T z. We follow some of the approximations
proposed by Thole: L 2,3 edges reduce to 2p → 3d
transitions, no attention is paid to 2p → s or d states
in the continuum and no hybridisation is taken into
account. From an analytical determination of hL zi, hS zi
and hT zi, one expects to obtain a better insight into
their relative intensities. This paper is very strongly
134 P. Sainctavit/Journal of Electron Spectroscopy and Related Phenomena 86 (1997) 133–138

inspired by a previous one that deals only with Cu 2+ From the ground state expression in Eq. (1), one
L 2,3 edges [9]. finds that
p
− 22cos2 v − 2 6cosv + 27sin2 v
hgs1lLz lgs1i = (4)
15
p
2+
2. The Cu ground state
− 11cos2 v − 4 6cosv − 9sin2 v
The initial state configuration of Cu 2+ is 2p 63d 9 and hgs1lSz lgs1i = (5)
30
the Hamiltonian is the sum of the electron kinetic p
− 22cos2 v − 7 6cosv − 63sin2 v
energy, the attractive electron–nucleus and repulsive hgs1lTz lgs1 . = (6)
electron–electron coulombic interactions, the crystal 105
field operator, spin–orbit coupling and Zeeman or Similar calculations for the excited states yield to the
exchange interaction. The parameters are the crystal computation of the intensities of L 2,3 edges, and a
field strength 10Dq, the spin-orbit constants z 3d and an straightforward application of the sum rules show
external or exchange magnetic field B. The magnetic that they are indeed analytically verified. This is no
field is set parallel to the (001) direction of the O h surprise, as we have made the same basic assump-
crystal field. The initial state lgs1i and its energy tions in our calculation as those adopted by Thole
1
Egs1 are et al. for their more general derivations.

1 3 3
lgs1 . = sinv lL = 2, S = , J = M = i
 −1
2 2 2
p 
−5
+ cosv plL = 2, S = , J = M = . − plL = 2, S = , J = M = …1†
1 5 3 5 1 5
i
6 2 2 2 2 6 2 2

0 r 1
p B − 11(4 + g)cos2 v
2
( − +
3(6 − g)sin2 vC
2 1 g)cosvsinv
10Dqcotv + mB BB C
3 6 3
= Eav + z 3d + @ + + A
1 i
Egs1 (2)
2 5 30 5 10

i
where Eav the average energy of the initial configura-
tion and m B is the Bohr magneton, m B = + 5.79 × 10 −5
eV T −1. The lLS,JMi phases in Eq. (1) are defined
following the Butler and Cowan notation [10,11]. v
is a parameter related to the ratio of z 3d/10Dq given by
the relationship
p
4 6
tg(2v) = −
25z 3d
2+
10Dq
with -(p/2) # v # 0 for the phase determination. In
Fig. 1 we have schematically represented the 10 Cu 2+
energy levels for different Hamiltonian symmetry.
3. The Ti 3+ ground state
When I communicated our results to Theo, he
found it interesting that hT zi might be non-zero and
he suggested that we examine the case with z 3d = 0. He
said that, in this case, exchange interaction should not
split the lowest lying twofold states belonging to
2
E g(O h). His strong intuition was correct, and he
(3)
also suggested that we check the case of 3d 1 (Ti 3+
or V 2+). I present here some numerical results. The
10 eigenstates building the 3d 9 configuration have
previously been given explicitly by M.-A. Arrio
[12]. The initial configuration of Ti 3+ is 3d 1 with all
the other shells filled. For the 10 wave functions of
 P. Sainctavit/Journal of Electron Spectroscopy and Related Phenomena 86 (1997) 133–138
Fig. 1. Scheme of energy levels for Cu 2+.
3d 1, we need to compute the matrix elements for elec-
tronic repulsions, spin–orbit coupling, octahedral
crystal field and Zeeman or exchange interaction.
These different 3d 1 matrix elements can easily be
determined from the corresponding elements of the
3d 9 configuration. From Cowan, eq. 11.58, one
sees that, if k . 0, h3d1 llU (k) ll3d1 i =
( − 1)k + 1 h3d9 llU (k) ll3d9 i, where U (k) is a spherical ten-
sor of rank k. The k = 0 terms of direct and exchange
integrals do not split the degeneracy of one configura-
tion so they do not need to be considered. The elec-
tronic repulsion matrix elements contain the product
of two such reduced matrix elements. The direct and
exchange matrix elements with k . 0 for Ti 3+ and
Cu 2+ are equal and their value is zero. The crystal
field matrix elements that split the configuration are
built with h3d 1 llU (4) ll3d 1 i reduced matrix elements.
Then the crystal field matrix elements for Ti 3+ are
opposite to those of Cu 2+. In contrast, Zeeman or
exchange interaction (k = 1) has the same matrix ele-
ments for Ti 3+ and Cu 2+. From Eq. 11.72 of Cowan,
one obtains hd1 llV (k1) ll3d1 i = ( − 1)k h3d9 llV (k1) ll3d9 i,
where V (k1) is a coupled spherical tensor of rank k
acting on space coordinates and of rank 1 acting on
spins. The matrix elements for spin–orbit coupling
(V (11)) for Ti 3+ have signs opposite to those for Cu 2+.
Fig. 2. Scheme of energy levels of the six lowest lying states for Ti 3+.
135
Despite these similarities between 3d 1 and 3d 9
(opposite matrix elements for spin–orbit and crystal
field, identical matrix element for Zeeman or
exchange matrix elements), the analytical calculation
for Ti 3+ is more complicated than for Cu 2+. Indeed, in
the case of Cu 2+, the lowest lying eigenvectors are
almost independent of the Zeeman or exchange inter-
action: the coupling through Zeeman or exchange
Hamiltonians of C 4h irreducible representations
(irreps) with different energies is not efficient because
it is small compared with the crystal field splitting.
This is not the case for Ti 3+, where the lowest lying
states are sixfold: 2T 2g. Without magnetic interaction
the Ti 3+ lowest lying states are U9(O h) and E0(O h),
split through spin–orbit coupling by < (3/2)z 3d.
Zeeman and exchange Hamiltonian couples two of
the four states of U9(O h) with the two states of
E0(O h): the symmetry of the ground state then
depends on the relative intensities of the two mag-
netic Hamiltonians. This is completely different
from the case of Cu 2+. We have reported in Fig. 2
the energy levels of Ti 3+ for z 3d = 0 and z 3d =
0.019 eV (its atomic value) and various Zeeman
or exchange interactions.
4. Discussion
It is found from Eq. (6) that hT zi can be non-zero in
octahedral symmetry. Care has to be taken with this
assertion. Indeed, if the total Hamiltonian is purely
octahedral, hT zi cannot be different from zero, and
the same holds also for hL zi and hS zi, since the irrep
J = 1 + of O 3 does not branch into the irrep A 1g of O h.
So hT zi = 0 in octahedral symmetry is obviously true,
136 P. Sainctavit/Journal of Electron Spectroscopy and Related Phenomena 86 (1997) 133–138
Fig. 3. (2/3)hS zi and (7/3)hT zi for Cu 2+ as a function of 10Dq.
Straight line: calculation at low temperature where the ground
state is almost pure lgs1i; broken line: calculation at room tem-
perature where the ground state is an almost equal mixture of lgs1i
and lgs2i (z 3d = 0.1 eV).
as it corresponds to a non-magnetised compound.2 In
magnetised compounds (i.e. the total Hamiltonian is
non-cubic) where only the crystal field is supposed to
be octahedral, which is the case for our Cu 2+ calcula-
tion, one finds that hT zi, in the same way as hL zi and
hS zi, can be non-zero. Moreover, it is found that the
contribution of hT zi almost always exceeds by a factor
of two the contribution of hS zi in the spin sum rule: for
L 2,3 edges of Cu 2+ hT zi can never be neglected. This
comes from the fact that T z is proportional to the m = 0
component of the W (21)1 Judd tensor [13]. This means
that T transforms like a spherical tensor of rank two
for the orbital part, a spherical tensor of rank one for
the spin part and a spherical tensor of rank one when
the spin and orbital parts are coupled. For T z to be
zero, one strong constraint is to suppose that T is zero.
This can be so when the irreps present in hgsl # lgsi
do not contain the irreps of T for the orbital, the spin
or the orbital and spin coupled part.
This can be clearly exemplified for the cases of
Cu 2+ and Ni 2+ in O h symmetry, where T transforms
like E g + T 2g for the orbital part, like T 1g for the spin
part and also like T 1g for the orbital and spin coupled
part. For Cu 2+, the ground state is built mainly from
the state ( 2E g)U g9. As the products hE gl(E g + T 2g)lE gi
for the orbital part, hE g9lT 1glE g9i for the spin part and
2
This is somewhat different from what P. Carra et al. said when
they studied the nullity of hT zi in magnetised compounds (i.e. the
total Hamiltonian is non-cubic) where only the crystal field is
supposed to be octahedral.
hU g9lT 1glU g9i for the orbit and spin coupled part all
contain the totally symmetric irrep A 1g, they are non-
zero. Then hT zi cannot be expected to be zero from
symmetry considerations and cannot be neglected
compared with hS zi in the spin sum rule. We have
… †
plotted in Fig. 3 the variations of 2=3 hgs1lSz lgs1i
… †
and 7=3 hgs1lTz lgs1i, which are the quantities pre-
sent in the spin sum rule of ref. [2] when 10Dq varies
from 0.1 eV up to 2 eV and z 3d = 0.1 eV (its atomic
… †
value). It is clear that 7=3 hgs1lTz lgs1i is almost
… †
always twice 2=3 hgs1lSz lgs1i. Similar considera-
tions for Ni 2+, whose ground state T 2g is mainly
built from 3A 2g, lead to the conclusion that hT zi should
be almost zero, as the product hA 2gl(E g + T 2g)lA 2gi
does not contain A 1g.
From Eq. (3), one finds that z 3d and 10Dq are
related to v by the ratio z 3d/10Dq and then no spin–
orbit coupling should be similar to a large crystal field,
although at 0 K there is an important difference: with-
out spin–orbit coupling (z 3d = 0) the ground state is
almost twofold degenerate, with eigenstates labelled
lgs1i and lgs2i; if spin–orbit coupling is switched on,
then the ground state is non-degenerate for any
applied magnetic field. In the case of B parallel to
(001), z 3dp 0 is equivalent topv
= < − 39.238 (i.e.
sin v = −… †
2=5 and cos v = … †
3=5 . In this case,
the average values of hL zi, hS zi and hT zi have to be
calculated over the two eigenvectors lgs1i and lgs2i.
One then finds that hL zi = 0, hS zi = − 1/2 and hT zi = 0
when v 3d = 0. In the real case the departure from no
spin–orbit coupling on the 3d shell can be linked to
the departure of v from − 39.238. In Eq. (3) one sees
that v is almost equal to − 39.238 if
… … †
z 3d =10Dq) p 2=25 or, equivalently, 10Dq q
1.25 eV when z 3d < 0.1 eV. This is never the case,
since the strongest 10Dq for Cu 2+ does not exceed 3
eV. Therefore in the case of Cu 2+ spin–orbit coupling
cannot be neglected compared with the crystal field,
and this departure from the no spin–orbit coupling
scheme is at the root of the non-nullity of hT zi. Indeed,
when z 3d Þ 0 and the external magnetic field B is
parallel to (001), the ground state is non-degenerate
and equal to lgs1i, with lgs2i lying at a slightly higher
energy.
Under the action of an external magnetic field B,
the two levels lgs1i and lgs2i are split by (hgs1lL z +
gS zlgs1i − hgs2lLz + gS zlgs2i)·B·m B, while under the
action of an exchange magnetic field B the two levels
 P. Sainctavit/Journal of Electron Spectroscopy and Related Phenomena 86 (1997) 133–138
Fig. 4. Energies of lgs1i and lgs2i for an external magnetic field B (in units of m B·B) and an exchange magnetic field B exch (in units
of g·m B·B exch). z 3d = 0.1 eV.
are split by (hgs1lgS zlgs1i − hgs2lgSz lgs2i)·B·m B. One
sees that an external magnetic field or an exchange
magnetic field splits the two levels by different
amounts of energy. In Fig. 4 we have represented
the energy splittings under an external magnetic
field or an exchange magnetic field as functions of
10Dq (takings z 3d = 0.1 eV). The action of the two
magnetic fields on the orbital part is rather different:
an external magnetic field acts directly on the orbital
variable through the L z operator, whereas an exchange
magnetic field acts only indirectly on the orbital vari-
ables through spin–orbit coupling. For identical exter-
nal and exchange magnetic fields, the splitting
between lgs1i and lgs2i due to the external magnetic
field will be much larger than the splitting due to the
exchange field. For most experiments, however, exter-
nal magnetic fields are limited to a few tesla (7 T with
a superconducting magnet on the SU22 beam line at
Orsay [14]), whereas in ferromagnetic or ferrimag-
netic compounds the exchange field is commonly lar-
ger than several tens of tesla. In the end the effective
splitting between lgs1i and lgs2i caused by external
and exchange fields is of similar amplitude. For a
numerical application one finds that, for B ext = 10 T
and B exch = 50 T, the total splitting between lgs1i and
lgs2i is 0.6 meV, equivalent to 8 K. One then expects
to see a large contribution of hT zi to the spin sum rule
for experiments performed at low temperature. At
137
room temperature the two states are almost equally
populated and hT zi < 0 (Fig. 3). We have also calcu-
lated numerically the expected values of hL zi, hS zi and
hT zi for a distorted octahedron around copper, where
the crystal field Hamiltonian requires three para-
meters, Dq, Ds and Dt [15]. It is found that in most
cases hT zi is large and almost always makes a larger
contribution to the spin sum rule than does hS zi.
The Ti 3+ calculations yield the same type of con-
clusion. For 10Dq = 1 eV and z 3d = 0.02 eV, hT zi is
non-zero at low temperature (below 10 K for a reason-
able external field) in the case of Zeeman interaction.
If only exchange interaction is considered, then hT zi Þ
0 even at quite a high temperature (below 30 K). One
important point concerning Ti 3+ is that, even when z 3d
= 0, hT zi Þ 0 if Zeeman interaction is present.
5. Conclusions
We consider that the understanding that can be
gained from such examples as Cu 2+ and Ti 3+ in octa-
hedral symmetry is essential for a better grasp of the
meaning of the magnetic dipole term hT zi, which is a
rather new operator whose nullity has been often
taken for granted. We have found that hT zi can be
large at low temperature (below 20 K) and cannot
be neglected even in a crystal field with octahedral
138 P. Sainctavit/Journal of Electron Spectroscopy and Related Phenomena 86 (1997) 133–138
symmetry. At room temperature hT zi tends to zero and
can then be neglected in the spin sum rules. We have
explained the origin of this effect and have particu-
larly emphasised the difference between an external
magnetic field and an exchange magnetic field. In
agreement with previous papers, we also account for
the fact that a decrease in the symmetry from octahe-
dral to a lower symmetry tends to give rise to a large
hT zi contribution that has to be calculated for the ana-
lysis of experiments at room temperature.
When writing such a paper, in which many formu-
lae rely on underlying approximations, we remember
Theo’s comments after noticing some considerable
and maybe unjustified approximation in one of our
previous work: ‘‘You can do very good physics with
wrong formulae’’.
Acknowledgements
This work was carried out jointly with Marie-Anne
Arrio and Christian Brouder. We thank M. Verdaguer
for comments about Cu 2+ compounds in octahedral
symmetry. We are glad, and sad, to acknowledge
our fruitful discussions with B.T. Thole.
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