Spin-orbital-entangled Jeff =1/2 state in 3d transition metal oxide

CuAl2 O4

Choong Hyun Kim

IBS-CCES & Seoul National University

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Orbital degeneracy and metal-insulator transitions

• Jahn-Teller (JT) distortion

[Wikipedia]

• Nonlinear molecule with a spatially degenerate electronic ground state will undergo a
distortion that removes degeneracy.

In (3d) transition metal oxides:

• Orbital degeneracy is lifted by distortions.
• Corresponding orbital ordering is expected.
• Orbital angular momentum is quenched by JT distortion.

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Atomic limit of t52g

• Atomic Hamiltonian of single hole in t52g : (λ: SOC, ∆:tetragonal crystal field)

H = λl · s + ∆l2z

eigenstate is: √
√
|ψ± i = α|lzeff = 0i|±i + 1 − α|lzeff = ±1i|∓i,
where |lzeff = 0i = |xyi, |lzeff = ±1i = − √1 (i|zxi ± |yzi).
2
: The solution becomes Jeff = 1/2 if ∆ = 0 in atomic limit.

dxy jeff = 12
dxy jeff = 12
F F
t2g
1
α = 1 : S = 1/2 dyz , dzx jeff = 32 α= 3 : Jeff = 1/2

λ∆ λ∆
Crystal Crystal
: ∆ (Crystal structure) will be determined by competition between JT, KK and SOC.

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A-site spinel CuAl2 O4

t2g 1
jeff = 2

3
jeff = 2
d9

eg

• Cubic A-site spinel (from single crystal X-ray) : No JT

• Cu2+ (3d9 ) with tetrahedral cage: t52g (not e3g )
• Spinel: Cu forms diamond lattice
• How Can we have Jeff = 1/2 with small SOC (∼0.05eV) in CuAl2 O4 ?

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Calculations Details

• First-principles density functional theory

• Elk
• PBEsol+SO+U
• 6×6×6 sampling to integrate BZ.
• Force criterion : 5×10−4 eV/Å
• Basis size was determined by RKmax =9.0

• Dynamical mean-field theory (DMFT)

• Single-site DMFT with exact diagonalization (ED) solver
• Wannier function tight-binding Hamiltonian from DFT full Cu 3d+oxygen 2p bands.
- t2g : DMFT
- eg : Hartree-Fock
- O 2p : non-interacting
- Full localized limit double counting scheme

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DFT Band structure without U

Without SOC With SOC

3 3
t2g jeff = 1/2
eg jeff = 3/2
2 2

1 1

0 0

1 1

2 2

3 3
L X W L K L X W L K

• tnn ∼0.03eV / tnnn ∼0.06eV

• Exchange energy (∼ t2 /U) would be very small.
• JT energy gain of tetrahedron would be relatively small. (crystal field is small.)

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 DFT+U(=7eV)+SOC energy landscape

√ √
|ψi = α|lzeff = 0i|±i + 1 − α|lzeff = ±1i|∓i
• Global minimum have cubic structure
1
60 with Jeff =1/2.
3
V/Vexp=0.97
2

40 jeff = 1/2 jeff = 1/2

1 jeff = 3/2 jeff = 3/2

Energy (eV)
V/Vexp=0.98
Energy(meV/f.u.)

20
1

2
1/3
0 V/Vexp=1.00 3
L X W L K PDOS (a.u.)

• A possible Jahn-Teller distorted S=1/2

state may stabilise under high pressure.
0.90
0.95 0.98
0
c/a 1.00 1.00 V/V exp

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DFT+U+SOC Phase diagram

U=7.0eV / 0=1.0
0.04 0.04
/ 0=0.4 U=5eV
/ 0=0.7 U=6eV
/ 0=1.0 U=7eV
0.02 0.02

Energy(eV/f.u.)

Energy(eV/f.u.)
0.00 0.00

0.02 0.02
0.90 0.92 0.94 0.96 0.98 1.00 1.02 0.90 0.92 0.94 0.96 0.98 1.00 1.02
c/a c/a

√ √
|ψi = α|lzeff = 0i|±i + 1 − α|lzeff = ±1i|∓i
α ∼ 1 : S = 1/2
1
α∼ : J = 1/2
3 eff

• The competition between SOC and JT results in the separation of two distinct solutions

• For a realistic set of parameters (U=7eV and λ/λ0 =1),

the Jeff =1/2 ground state appears at c/a=1.

• The strong correlation helps the small SOC of the Cu d-orbital to overcome the JT distortion.
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Dynamical mean-field theory spectra

U=7.0, JH =1.0, λ=0.05

• Jeff =1/2 state survives under quantum fluctuations.

• Paramagnetic insulating phase is stablized. (consistent with experiment.)
• Separation between jeff = 1/2 and jeff = 3/2 are not clear.
- Occupied states are governed by t42g multiplet structure.

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Atomic multiplets of t42g : LS vs jj coupling scheme

LS coupling jj coupling

JH  λ λ  JH
1
S0
Jeff = 0, 2

3JH 3
2λ

Jeff = 1, 2
1
D2
3
2λ
2JH

3
Jeff = 0
P0,1,2
CuAl2O4 iridates

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Dynamical mean-field theory spectra: t2g only model

U=7.0, JH =1.0, λ=0.05

• CuAl2 O4 : hole spectra are
described by LS-coupling limit.

U=1.8, JH =0.15, λ=0.50 • Iridates : spectra are very similar to

single-particle jj-coupling scheme.

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Summary

• We report the theoretical evidences for the Jeff =1/2 ground state in CuAl2 O4 .

3
1
60
V/Vexp=0.97
2

jeff = 1/2 jeff = 1/2

40
1 jeff = 3/2 jeff = 3/2

Energy (eV)
V/Vexp=0.98
Energy(meV/f.u.)

20 0

1/3 1
0 V/Vexp=1.00

0.90
0.95 0.98 3
0
c/a 1.00 1.00 L X W L K PDOS (a.u.)
V/V exp

• Density functional theory combined with dynamical mean field theory calculations reveal that
the Jeff =1/2 state survives the competition with the orbital-momentum-quenched S=1/2 state
with the help of strong electron correlation.

• The five electrons in t2g levels compose many-body multiplets, whereas the unoccupied single
hole is well described by the non-interacting jeff =1/2 state, leading to unique excitation spectra.
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