The document summarizes the LDA+U method for treating strongly correlated materials and applies it to two cases - CaFeO3 and La1/2Sr2/3FeO3. LDA+U adds an on-site Coulomb interaction term U to the LDA functional to better describe localized d-orbitals. It shows how LDA+U predicts charge disproportionation and an insulating state in both materials, driven by factors like lattice distortions, correlations, and disorder.

1. Strongly correlated electrons: LDA+U in
practice
Tanusri Saha-Dasgupta
Dept of Condensed Matter Physics & Materials Science
Thematic Unit of Excellence on Computational Materials Science
S.N. Bose National Centre for Basic Sciences
Salt Lake, Calcutta, INDIA
tanusri@bose.res.in
. – p.1/45

2. Outline
• Introduction: why strong correlations ?
- Failure of one-electron theories
- Examples of strongly correlated materials
- Different energy scales and MIT in TMO
• Methods to deal with correlations in realistic ways
- Concepts (LDA+U)
- Practical details
- Example of CaFeO3 and La1/2Sr2/3FeO3
. – p.2/45

3. Electronic Structure Calculations:
• Good description of many microscopic properties are obtained in
terms of -
Born-Oppenheimer Approximation
Nuclei and the electrons to a good approximation may be treated
separately.
One-electron Approximation
Each electron behaves as an independent particle moving in the
mean field of the other electrons plus the field of the nuclei.
. – p.3/45

4. LDA
Most satisfactory foundation of the one electron picture is provided
by the local approximation to the Hohenberg-Kohn-Sham density
functional formalism
≡ LDA
⇓
• LDA leads to an effective one electron potential which is a function
of local electron density.
• Leads to Self consistent solution to an one electron Schrödinger
Eqn.
. – p.4/45

5. Flow-chart for LDA self-consistency
First principles information: atomic no., crystal structure
⇓
Choose initial electron density ρ(r)
Calculate effective potential through LDA:
Veff (r) = Vion(r)+ d3
r′
Vee(r−r′
)ρ(r′
)+ δExc[ρ]
δr
Solve K-S eqns:
[−∆+Vion(r)++ d3
r′
Vee(r−r′
)ρ(r′
)+δExc[ρ]
δr ]φi(r) = ǫiφi(r)
Needs to expand K-S wavefunctions in terms of basis, Φilm
Calculate charge density: ρ(r) = |φi(r)|2
Iterate to selfconsistency
⇓
Total energy, inter-atomic forces, stress or pressure, band struc-
ture, . . . . – p.5/45

6. Strongly correlated electron materials
∗ The conventional band-structure calculations within the framework
of LDA is surprising successful for many materials.
∗ However, they fail for materials with strong e-e correlation !
• correlation effect necessarily arise, and
• the consideration of electron correlation effects provides the
natural way to understand the phenomena like the insulating nature
of CoO.
. – p.6/45

7. Strongly correlated electron materials
Energy
k
ρ (εF) = 0
Even No. of e’s
per unitcell
ρ (εF) = 0
ρ (εF) = 0
Odd No. of e’s
per unitcell
Ca, Sr
Energy
k
C
Energy
k
Ef
Na, K
Ef
Even No. of e’s
per unitcell
+ band overlap
Predictions from LDA (Bandstructure)
Accordingly to LDA, odd no. of e’s per unit cell always give rise to Metal ! . – p.7/45

8. Strongly correlated electron materials
Failure of Band Theory
Total No. of electrons = 9 +6 = 15
Band theory predicts CoO to be
metal, while it is the toughest
insulator known
−−) Importance of e−e interaction effects (Correlation)
Failure of LDA −) Failure of single particle picture
. – p.8/45

9. Strongly correlated electron materials
e
+ U3s
ε
3s
−
NaNa
+ −
0 ε
3s2
NaNa
0 0
ε
3s
energy
a (lattice constant)a0
2s
2p
3s
itinerant localizedenergy/atom
3s 3s/ tU
3s
ε
3s−At
3s
ε
H_3s = H_band + H_columb
. – p.9/45

10. Examples of strongly correlated materials
Transition metals:
- d-orbitals extend much further from the nucleus than the core
electrons.
- throughout the 3d series (and even more in 4d series), d-electrons
do have an itinerant character, giving rise to quasiparticle bands!
- electron correlations do have important physical effects, but not
extreme ones like localization.
. – p.10/45

11. Examples of strongly correlated materials
f-electrons: rare earths, actinides and their compounds:
- rare-earth 4f-electrons tend to be localized than itinerant,
contribute little to cohesive energy, other e- bands cross EF , hence
the metallic character.
- actinide (5f) display behavior intermediate between TM and rare
earths
- e- correln becomes more apparent in compounds involving
rare-earth or actinides.
- extremely large effective mass → heavy fermion behavior.
- At high temp local mag. mom and Curie law, low-temp screening
of the local moment and Pauli form → Kondo effect
. – p.11/45

12. Examples of strongly correlated materials - TMO
- direct overlap between d-orbitals small, can only move through
hybridization!
4
t2g
eg
10
2
2
4
2
2
2
d x2−y2
d 3z2−r2
2
2
2
d xy
d zx
d yz
Free Atom Cubic Tetragonal Orthorhombic
6
Crystal Field Splitting
. – p.12/45

13. Examples of strongly correlated materials- TMO
p σ
p π
2g
t
ge
d x2−y2 d x2−y2d x2−y2
d xy d xy
Ligands (orbitals p/O)
Hybridization via the
d xy d xz d yz
d 3z2−r2 d x2−y2
. – p.13/45

14. Examples of strongly correlated materials - TMO
Three crucial Energies
tpd Metal-ligand Hybridization
∆ = ǫd − ǫp Charge Transfer Energy
U On-site Coulomb Repulsion
Band-width is controlled by: teff = t2
pd/∆
. – p.14/45

15. Examples of strongly correlated materials - TMO
The infamous Hubbard U
Naively: φ∗
i↑φi↑
1
|r−r′|φ∗
i↓φi↓
But this is HUGE (10 -20 eV)!
SCREENING plays a key role, in particular by 4s electrons
- Light TMOs (left of V): p-level much below d-level; 4s close by : U
not so big U < ∆
- Heavy TMOs (right of V): p-level much closer; 4s much above
d-level : U is very big U > ∆ . – p.15/45

16. Examples of strongly correlated materials - TMO
The Mott phenomenon: turning a half-filled band into an insulator
Consider the simpler case first: U < ∆
Moving an electron requires creating a hole and a double
occupancy: ENERGY COST U
This object, once created, can move with a kinetic energy of order of
the bandwidth W!
U < W: A METALLIC STATE IS POSSIBLE
U > W: AN INSULATING STATE IS PREFERRED
. – p.16/45

17. Hubbard bands
d p∆ = | ε − ε |
Energy
p band
d band
U
Interaction U
The composite excitation hole+double occupancy forms a band (cf
excitonic band)
. – p.17/45

18. Charge transfer insulators
d p∆ = | ε − ε |
t
pd
t
eff
t
pdGain: ~ / ∆
2
Cost: ∆ = ε − ε
d p
Energy
d band
Heavy TMOs
p band
Fermi level
Interaction U
charge gap
Transition for ∆ >
Zaanen, Sawatzky, Allen; Fujimori and Minami
U
. – p.18/45

19. Methods
Strongly correlated Metal
LDA gives correct answer
U < W
Weakly correlated Metal
Intermediate regime − Hubbard bands +
QS peak (reminder of LDA metal)
?
U >> W
Mott insulator
Can be described
by "LDA+U" method
courtesy: K. Held
. – p.19/45

20. Methods
LDA gives correct answer
U < W
Weakly correlated Metal
U >> W
Mott insulator
Can be described
by "LDA+U" method
. – p.20/45

21. Basic Idea of LDA+U
PRB 44 (1991) 943, PRB 48 (1993) 169
• Delocalized s and p electrons: LDA
• Localized d or f-electrons: + U
using on-site d-d Coulomb interaction (Hubbard-like term)
U i=j ninj
instead of averaged Coulomb energy
U N(N-1)/2
. – p.21/45

22. n+1 n−1
n n
n+1 n−1
U
e
Hubbard U for localized d orbital:
U = E(d ) + E(d ) − 2 E(d )
n
. – p.22/45

23. LDA+U energy functional (Static Mean Field Theory):
ELDA+U
local = ELDA
−UN(N − 1)/2 +
1
2
U
i=j
ninj
LDA+U potential :
Vi(ˆr) =
δE
δni(ˆr)
= V LDA
(ˆr) + U(
1
2
− ni)
. – p.23/45

24. LDA+U eigenvalue :
ǫi =
δE
δni
= ǫLDA
i + U(
1
2
− ni)
For occupied state ni = 1 → ǫi = ǫLDA
− U/2
For unoccupied state ni = 0 → ǫi = ǫLDA
+ U/2
⇓
∆ǫi = U MOTT-HUBBARD GAP
U = δ
δnd
LDAε
ε
LDA
. – p.24/45

25. Issues of Double Counting
. – p.25/45

26. Issues of Double Counting
. – p.26/45

27. Issues of Double Counting
. – p.27/45

28. Rotationally Invariant LDA+U
LDA+U functional:
ELSDA+U
[ρσ
(r), {nσ
}] = ELSDA
[ρσ
(r)] + EU
[{nσ
}] − Edc[{nσ
}]
Screened Coulomb Correlations:
EU
[{nσ
}] =
1
2
{m},σ
{ m, m
′′
|Ve,e|m
′
, m
′′′
nσ
mm′ n−σ
m′′
m′′′′ +
( m, m
′′
|Ve,e|m
′
, m
′′′
− m, m
′′
|Ve,e|m
′′′
, m
′
nσ
mm′ nσ
m′′
m′′′′
LDA-double counting term:
Edc[{nσ
}] =
1
2
Un(n − 1) −
1
2
J[n↑
(n↑
− 1) + n↓
(n↓
− 1)]
. – p.28/45

29. Slater parametrization of U
Multipole expansion:
1
|r − r′
|
=
kq
4π
2k + 1
rk
<
rk+1
>
Y ∗
kq(ˆr)Ykq(ˆr
′
)
Coulomb Matrix Elements in Ylm basis:
mm
′
||m
′′
m
′′′
=
k
ak(m, m
′′
, m
′
, m
′′′
)Fk
Fk
→ Slater integrals
Average interaction: U and J
U = F0
; J (for d electrons) = 1
14 (F2
+ F4
)
. – p.29/45

30. Issues of Double Counting
. – p.30/45

31. Issues of Double Counting
. – p.31/45

32. How to calculate U and J
PRB 39 (1989) 9028
• Constrained DFT + Super-cell calculation
• Calculate the energy surface as a function of local charge
fluctuations.
• Mapped onto a self-consistent mean-filed solution of the
Hubbard model.
• Extract U and J from band structure results.
. – p.32/45

33. Notes on calculation of U
• Constrained DFT works in the fully localized limit. Therefore
often overestimates the magnitude of U.
• For the same element, U depends also on the ionicity in different
compounds → higher the ionicity, larger the U.
• One thus varies U in the reasonable range (Comparison with
photoemission..).
Better or more recent approach: Constrained RPA method
See e.g.
http://icts.res.in/media/uploads/Talk/Document/AryasetiawancRPA.pdf
for details.
. – p.33/45

34. Where to find U and J
PRB 44 (1991) 943 : 3d atoms
PRB 50 (1994) 16861 : 3d, 4d, 5d atoms
PRB 58 (1998) 1201 : 3d atoms
PRB 44 (1991) 13319 : Fe(3d)
PRB 54 (1996) 4387 : Fe(3d)
PRL 80 (1998) 4305 : Cr(3d)
PRB 58 (1998) 9752 : Yb(4f)
. – p.34/45

35. CO and Insulating state in CaFeO3,
La1/3Sr2/3FeO3
TSD, Z. S. Popovic, S. Satpathy
Phys. Rev. B 72, 045143
. – p.35/45

36. CaFeO3
2g
13
g
JT Instability
(cf: LaMnO )3
Charge Disproportionation
Mn−O covalency Fe−O covalency
Whangbo et al, Inorg Chem (2002)
Fe 4+ (t e ) HIGH SPIN STATE
CaFeO3 Ca
O 2−
2+ Fe 4+
Unusual high valence state of Fe
NOMINAL VALENCE CONSIDERATION:
. – p.36/45

37. CaFeO3
. – p.37/45

38. . – p.38/45

39. LDA+U band structure
. – p.39/45

40. 2g+O(p)t
Fe(A)−eg
Fe(B)−eg
. – p.40/45

41. Hubbard U instead of Stoner I
. – p.41/45

42. La1/3Sr2/3FeO3
2+
3
La Sr FeO
1/3 2/3
Sr
O 2−
La 3+
Fe 3.67+
z
yx
NOMINAL VALENCE CONSIDERATION:
3 x Fe 3.67+
2 x Fe 3+ + 1 x Fe 5+
2 x Fe 4+ + 1 x Fe 3+
(AFM Insulating)(PM Metallic)
T
direction
[111] pseudo−cubicFeB
CDW of 3−fold periodicity
+ SDW of 6−fold periodicity
Neutron Diffraction (Battle et a.’90):
No sign of structural modulation
Electron Diffraction (Li et al, ’97):
Evidence of structural modulation
FeA
[Mossbauer data, Takano et. al.]
. – p.42/45

43. La1/3Sr2/3FeO3
. – p.43/45

44. La1/3Sr2/3FeO3
. – p.44/45

45. Summary
∗ Charge disproportionation in CaFeO3, driven by lattice distortion.
Insulating property needs the assistence from correlation.
∗ Charge disproportionation and insulating state in La1/2Sr2/3FeO3
driven by correlation, magnetism and disorder.
∗ Lattice of La1/2Sr2/3FeO3 reacts to the charge modulation.
. – p.45/45