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atomic energies is due to the apparition of a perturbation pendent on the spin σ and the bands energies are shifted
potential ∆U (r). This scheme can be used as a numeri- by an exchange splitting energy term :
cal correction for the screening effects. t also takes into
account also the hopping integral t0 . The overlap with Ud µ
∆ = = Id−d µ (4)
the neighbors open a band energy a width W which de- n0
scribes the allowed energies for the d electrons to hop Where Id−d is the Stoner parameter. The local hamilto-
from a site i to a site j. nian can be written as :
Z
X Ud n2d µ2
W ∝ t 0 = − ψm ∗
(r)∆U (r)ψm (r − Rm )d3 r (3) nUd σ Ud µ †
H= k + − ckσ ckσ − −
2n0 2 n0 n0 4 4
kσ
The interatomic exchange is symbolized in the equation (5)
(1) by the creation and the annihilation operators. The We can deduce the Stoner relation (4) intuitively by sup-
Hubbard local hamiltonian (1) in the Hartree-Fock de- posing that the magnetism comes from an augmentation
scription gives an effective repulsion Ud which contains of the population of the majority spin on an atomic site
the intra-atomic Hartree term and the exchange. We can compared to the minority spins. The atomic potential is
describe the screening effects induce by the s charge on then modified by the unpaired µ electrons making lost
the d band as the d electrons are feeling an additional Ud µ in the Coulomb energy. In our perturbation ap-
effective repulsion Udxc per orbital (Containing an extra proach the atomic levels are then shifted by αm = −∆
xc xc
exchange coupling Jd−d and the Hartree repulsion Ud−d for the electrons in the majority spin towards the lower
in the d orbital). energies (because the Coulomb potential is weaker) com-
X † X pared to the minority spin and the band structure has no
H = −t ciσ cjσ + h.c. + UdHF nλ↑ nλ↓ symmetry of spin anymore. The system lost in cohesion,
i,j,σ λ but win in magnetic energy. We can easily relate ∆ with
X
+Udxc nλ↑ nλ↓ the intra-orbital exchange Jd−d (Here ∆ is proportional
λ to µ2 not as in the reference [11]) :
The eigenstates of this hamiltonian in the d band are ∆
quite similar to those obtained by solving the Kohn-Sham ∆ = n0 · Jd−d · µ2 and Jd−d = (6)
n0 · µ2
3
For the iron the weak ferromagnet, we will use ∆ = exact exchange-correlation in the energy to take into ac-
2n0 · Jd−d · µ2 . In this document we will not deal with count the modification of the electronic structure.
the spin transport properties and the spin-orbit coupling. "Z
EF Z EF #
If we do the summation in the hamiltonian (5) we will 1
Ud = End (E, Ne − 1)dE − End (E, Ne )dE
find the difference in the total cohesive energy when we 2 −∞ −∞
go from a non magnetic state to a magnetic state : −UdΣ
mag. f erro non mag.
∆E = Ecoh − Ecoh It is finally possible to deduce the exchange coupling Jd−d
= ∆Ecoh − 4n1 0 Ud µ2 (delocalized) from the expression (6). The Curie temperature will be
calculated using the Stoner-Weiss model [14].
= ∆Ecoh − 4n1 0 Udlocal µ2 − 4n1 0 Udxc µ2 (localized)
The exact exchange-correlation energy gives the correc- Jd−d µ2ef f
Tc ≈ (7)
tion in a localized case (without the screening) with an 3kB
additional repulsive term Udxc . In the delocalized case
(with the sp state) this term is already included in Ud .
It is then possible to deduce the electron-electron interac- III. RESULTS
tion parameters : the Hubbard effective repulsion, the ex-
change coupling Jd−d and the exchange-correlation U xc .
In a strong formalism we should study these phenom- 2.5
ena with the Green’s functions taking into account the nd (E) localized
screening effects. But for the sake of the simplicity, we nd (E) delocalized
2
can deduce these parameters directly by the local den-
sity of states (LDOS) n(E). The advantage of the tight-
1.5
LDOS
binding model is the fact that this approach allows to
decompose the LDOS in different components. Then we
can diagonalize the 5 × 5 hamiltonian with the hopping 1
parameter in the d band (ddσ, ddπ, ddδ) and obtain a
LDOS nlocal
d (E) of localized d electrons without the sp
0.5
state. To treat the delocalized structure, we need to di-
agonalize all the 9×9 hamiltonian including the sp states
for getting a partial delocalized d LDOS ndeloc.
d (E). Gen- 0
erally, every variation in the electronic occupation leads −10 −8 −6 −4 −2 0 2 4
to the apparition of a Coulomb term which modifies the Energy E − Ef (eV)
band energy as stated previously. Then we can find every
creation or annihilation of a coulomb energy by making FIG. 1. Comparison of LDOS in a local d band and non
the difference of the band or the cohesive energy in the local d band
localized and the delocalized d bands.
Z EF Z EF By using the hopping parameters given in the refer-
xc deloc.
Ud = End (E)dE − Enlocal
d (E)dE ence [15] along with our own hopping parameters, we
−∞ −∞
calculated the (LDOS) in the delocalized d band and a
This simple expression describes the exact exact echange- localized d band. The figure (1) shows that in the lo-
correlation per d orbital. To be more accurate numeri- calized case the bandwidth is weak and the density of
cally it is better to use the variation of the cohesive en- states is high. Every state is occupied on average by
ergy to avoid some shifts in the atomic energy by the more than one electron showing an almost double occu-
fitting. We find in our calculations for the iron BCC, pation of a local electronic structure, describing strong
the Cobalt CFC and the Nickel CFC respective values : bounded system in the Hartree-Fock picture. This is not
1.3 eV, 1.55 eV and 2.2 eV. These values are quite simi- the electronic structure of the d band of a metal (we will
lar to those obtained for the effective Coulomb repulsive see later that it is the ground state of a metal oxide with-
term Ud in the reference [12] we will explain why later. out a crystal field splitting) and all the energies are then
In the same manner we can find the Hubbard parameter wrong without an appropriate correction. But in the
Ud by calculating the difference in the band energy of a case of the delocalized d LDOS (with the sp states) the
d orbital with Ne electrons and a d orbital with Ne − 1 bandwidth is wide by the screening effect induced but
electrons. But this calculation is known to give a value the s state making the occupation on average by only
of Ud about 10 eV or 20 eV with the method in the refer- one electron which corresponds to the description of the
ence [13]. This leads also to the fact that we neglect the exchange-correlation hole and describes the ground state
exchange-correlation. Remove an electron can be seen in a metal.
as a creation of a hole which screens the local electronic To find our values of µ, ∆, we shift the rigid band
structure, so in the same picture we should reduce the with successive values of ∆ conserving the charge in the
4
d band until we obtain the coherent magnetic moment 6.63 eV for getting the good magnetic moment (Tableau
(described in the reference [9]). This approach is the fit II).
of two curves represented by :
5 TABLE II. Electron-electron interaction parameters calcu-
µ(∆) = n↑d − n↓d and µ(∆) = ∆ (8) lated in a delocalized d band
U
Fe BCC Co CFC Ni CFC
This process which can appear approximate is quite ac-
U local [eV] 6.10 6.09 6.63
curate since we will find the exact correlations (∆, U )
∆ [eV] 2.76 1.87 0.81
which gives a the correct magnetic moment. We found Jd−d [eV] 0.054 0.14 0.44
in the localized d band 3.01 eV for the effective repulsion Tc [K] 1065 1350 632
Ud in the Cobalt CFC. This value is obtained by shifting
the LDOS by an exchange splitting energy of ∆ = 0.93
eV to get a coherent magnetic moment of µ = 1.55 µB These values which seems overestimated are the real
(excluding the orbital magnetic moment about 0.12 µB values of the effective repulsion because they contain the
[16]). This value of ∆ is in agreement with photoemis- screening effects and we obtain an accurate Curie temper-
sion experiments of 1 eV [17–19]. Likewise, in the Iron ature and the exchange coupling. The only way to annihi-
and the Nickel we found respectively Ud = 3.78 eV and late this screening potential and the exchange-correlation
Ud = 2.2 eV by splitting the LDOS with 1.63 eV and effect is to add an electronegative element. In fact, in
0.26 eV. Values in agreement with some photoemission metal oxide, the delocalized sp charge is bonded and then
results [20, 21] and now we have a coherent magnetic localized in the p state so that the exchange-correlation
moment of 2.2 µB in the Iron and 0.61µB in the Nickel. hole is annihilated. The localized d band (without sp
The exchange coupling and the Curie temperature are screening) then describes perfectly the metal oxides and
calculated using the expressions (6) and (7). the Kohn-Sham equations with an exchange-correlation
term for the d band will always describes these oxides as
a metal. A metal oxide is then paradoxically a weakly
TABLE I. Electron-electron interaction parameters and the correlated system. This gap is a coulomb energy barrier
Curie temperature calculated in a localized d band to delocalize the d electron which can be express by :
Fe BCC Co CFC Ni CFC
Udlocal [eV] 3.78 3.01 2.2 Eg,dr = Udnon local − Udlocal (9)
µ [eV] 2.20 1.55 0.61
∆ [eV] 1.63 0.93 0.26 The direct gaps for the NiO, FeO et CoO are respec-
Jd−d [eV] 0.03 0.07 0.14 tively 2.05 eV, 3.1 eV et 4.43 eV. The transition from
Tc [K] 561 701 201 the localized to the delocalized state can then be ther-
mally activated, we will not study these Mott transition
in this paper. It is then finally possible to change the
We obtain an inaccurate description of the magnetic basis from a localised basis to a delocalized basis by the
system, with the Curie temperature almost the half of simple relation :
the experimental Curie temperature due to the almost
double occupation, the magnetic energies are also under- Udlocal = Udnon local − 2Udxc
estimated [6] and this system is known to give a surface
| {z }
Gap
energies half of the experimental surface energies. The
agreement with the experimental results for the exchange This relation gives the link between the localized d band
splitting ∆ and the effective repulsion Ud is due to the and the partial delocalized d band. The gap is therefore
fact that the exchange-correlations are not taking into given by Eg,dr = 2·U xc and the exact echange-correlation
account in the energy balance when the experimentalists energies from the experimental gaps are 1.2 eV, 1.4 eV
treats the photoemission spectrum. This model shows and 2.15 eV for Fe, Co and the Ni respectively and for
another characteristic, if we consider our atomic configu- all the d orbitals ( Udxc (total) = n0 × Udxc ) : 6 eV, 7 eV
ration, in this strong bonded model γ = 3, 2 and 1 elec- and 10.75 eV which corresponds to the corrections using
trons engaged in to form the bonds for the Co, Fe and Ni a LDA+U or a GGA+U.
in the d shell to get the stability. With the results of the
Table (I) we can define the exact exchange-correlation
energy as the effective repulsion in one orbital d by the IV. CONCLUSION
itinerant electrons giving the relation : U xc = Udlocal /γ.
That is the reason why in the reference [12] gives the ex- The interactions between electrons are fundamental in
act exchange-correlation energy. In the case of the delo- the solid state physics, there are always problematic be-
calized d band, we found for the exchange splitting in the cause the electrons behaviors are not really predictable.
iron, Cobalt and the Nickel respectively 2.76 eV, 1.87 eV As the electron-electron interactions depends on the final
(comparable to another calculation [22]) and 0.76 eV and occupation gives the fact that maybe we will never solve
the Hubbard parameter Ud about 6.10 eV, 6.09 eV and the many-body Schrödinger equation analytically. But
5
we can deduce interaction parameters between electrons to build a new model which will take into account the lo-
as showed in this work and elaborate a semi-empirical calized and the delocalized effects instead of dealing with
model accurate and faster than calculations based on the several functionals and approximations for some special
first principles and extend our study to complex materi- systems. But waiting, although the corrections by quan-
als. In this paper, all the electronic structure of a metal tifying the correlations give a coherence and the unifica-
and an oxide is due to localization or the delocalization tion of many models. As we saw, to study a metal, we
of a single s electron. The screening induce by this sp ought to use a delocalized d band otherwise we cannot
state should be investigated in a strong formalism with describe correctly the energies and we are not dealing
the green’s functions, giving the way to describe analyt- with a transition metal d band but a metal oxide. Some
ically the exact exchange-correlation and the possibility corrections by shifting the atomic levels or adding a re-
pulsive term are then compulsory.
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