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Accurate effective masses from first principles

Conference Paper · April 2015

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2 authors:

Jonathan Laflamme Janssen X. Gonze

Université Catholique de Louvain - UCLouvain Université Catholique de Louvain - UCLouvain
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Accurate effective masses from first principles

Jonathan Laflamme Janssen* and Xavier Gonze

Institute of Condensed Matter and Nanosciences (IMCN/NAPS), Université
catholique de Louvain
*jonathan.laflamme@uclouvain.be
 Effective masses

• design materials with better mobility 


for electronic applications
• organic semiconductors
• next generation CPUs
• transparent conducting oxides (TCOs)

better µ : both higher conductivity and transparency

current standard: ITO. But In shortage…

2
k
ε kn ≈ ε Γn + M ≠1
2M
−1
ε kn ≈ ε Γn + k M Γn k (3D)
1
2
T

∂ εn
(M )
2
−1 αβ αβ
= ≡ εn
n
∂kα ∂kβ

Abinit Developper workshop, Liège, Belgium, April 29, 2015 2 of 15

 What’s missing?

Effective masses calculation

Traditional: This project:
ε k+Δ k, n − ε k, n
• finite 
 ε αβ
k,n ~2 • density functional 

Δk
2
differences perturbation theory (DFPT)



• numerical noise 

• extra convergence

(
• Mn )
−1 αβ
=ε αβ
n when degenerate • accurate calculation of M n
−1

• density functional theory • include interactions:

• poorly assessed accuracy
 • electron-electron (GW)


• electron-phonon

Abinit Developper workshop, Liège, Belgium, April 29, 2015 3 of 15

 DFPT

Direct calculation of effective masses:

∂ εn
(M )
2
−1 αβ
= αβ
≡ εn αβ = { xx, yy, zz, xy, yz, xz}
n
∂kα ∂kβ
αβ
= ψ n Ĥ ψ n
αβ
= ψ n Ĥ ψn
+ ψ ( α
n
β
Ĥ ψ n + α ↔ β + cc. )
α β
+ ψ n Ĥ − ε n ψ n + cc.

( Ĥ − ε ) ψ
n
α
n (
= Ĥ − ε α α
n )ψ n

2nd order Ĥ derivative

Abinit Developper workshop, Liège, Belgium, April 29, 2015 4 of 15
 /
Derivatives of Ĥ

=
( k + G)
2

δ GG ' + VG−G ' + V!k,GG '

G Ĥ k G ' DFT: r V̂ r ' = V (r)δ (r − r ')
2
ˆ
pseudo: r V r ' = V! (r,r ')
!

G Ĥ G ' = ( k + G )α δ GG ' + 0 + Vk,GG '

α
k
! α

G Ĥ αβ ! αβ
G ' = δ αβδ GG ' + 0 + Vk,GG '
k

G Vk G ' = ∑ k + G pi Dij p j k + G '

ˆ
!
ij
⎛ k + G ⎞ rc
k + G pi ∝ e i(k+G )⋅r
Yli mi ⎜ ⎟ ∫ dr pi (r) jli ( k + G r )
⎝ k+G ⎠ 0

Abinit Developper workshop, Liège, Belgium, April 29, 2015 5 of 15

 Results

Si, 1st band, Γ

Finite DFPT Δ
1.161 0.000 0.000 1.161 0.000 0.000 3E-09 1E-07 7E-08
0.000 1.161 -0.000 0.000 1.161 0.000 1E-07 9E-08 1E-11
0.000 -0.000 1.161 0.000 0.000 1.161 7E-08 1E-11 2E-07

Si, 1st band, 1

2 X
−4
Δ = 10
Ge, 1st band Γ , 1 2 X

Abinit Developper workshop, Liège, Belgium, April 29, 2015 6 of 15

 Numerical noise : finite differences

αβ
ε k+Δ k, n − ε k, n
ε k,n ~2
Δk
2

• Δk convergence

cumbersome

Abinit Developper workshop, Liège, Belgium, April 29, 2015 7 of 15

 Numerical noise : DFPT

• One less (cumbersome) convergence

Abinit Developper workshop, Liège, Belgium, April 29, 2015 8 of 15

 Degenerescences?
• Degenerate perturbation theory:
• in degenerate subspace, diagonalize Ĥ αβ
• But cannot diag. w/r to 6 perturbations! αβ = { xx, yy, zz, xy, yz, xz}
αβ −1 −1
n Ĥ n' ≠ 0 ⇒ M n → M nn' Luttinger and Kohn, Phys Rev 97 869 (1955)

• Around band extrema

1 T −1 k2 k 2
ε nn′ (k) ≈ k M nn' k = k̂(θ , φ )T M −1 k̂(θ , φ ) = M nn' (θ , φ )
−1
2 2 nn'
2
2
k
ε n (k,θ , φ ) ≈ M n−1 (θ , φ )
2
• M n (θ , φ ) not convenient for transport properties calculation
• n
M (θ , φ ) → σ n → M n
eqv
Mecholsky et al., PRB 89 155131 (2014)

Abinit Developper workshop, Liège, Belgium, April 29, 2015 9 of 15

 Launching a run

• Must be done within a DDK calculation (rfelfd 2)

• Triggered using

efmas 1

efmas_band (band to be trated)

efmas_ntheta (# points for numerical integration) (degenerate case)

• Currently require

ieig2rf 1

useylm 1

• For an example, see tests/v7/Input/t80.in

Abinit Developper workshop, Liège, Belgium, April 29, 2015 10 of 15

 Future directions
• LDA underestimate effective masses
• Refine electron-electron interaction
⎛∇ 2
⎞
⎜⎝ 2 + Vext (r) + VH (r) + Vxc (r)⎟⎠ ψ kn (r) = ε knψ kn (r) DFT

Vxc (r)ψ kn (r) → ∫ dr ' Σ(r,r ', ε kn )ψ kn (r ') G0W0 Σ̂ Exact e-e

( )
Δε kn = ψ kn Σ̂ ε kn + Δε kn − V̂xc ψ kn {ε kn , ψ kn } Γ̂ GW

∂ Σ̂ (ω )
( )
≈ Σ̂ ε kn − V̂xc +
∂ω ε
Δε kn P̂ Ŵ

Σ̂ ( ε ) − V̂
kn
{
DFT ε kn , ψ kn }
≈
kn xc
( )
≡ Z Σ̂ ε kn − V̂xc
∂ Σ̂ (ω )
1−
∂ω ε
kn

Abinit Developper workshop, Liège, Belgium, April 29, 2015 11 of 15

 Future directions

• Correction factor for e-e interactions

∂ 2 ε DFT
M G 0 W0
∂k ∂ε 2 DFT
= 2 G0 W0 = G0 W0
M DFT
∂ ε ∂ε
∂k 2

<0.02% M in AlAs Oshikiri et al. PRB 66 125204 (2002)

∂ Σ̂ (ω ) ∂ Σ̂ (ω )
∂ε G 0 W0
= ∂ε DFT
+ δk + δε G 0 W0 ~16% M in AlAs
∂k ∂ω

∂ε DFT ∂ Σ̂ (ω ) 1 M G 0 W0
= 1− = =
∂ε G 0 W0
∂ω Z M DFT

• How general is this apprx?

Abinit Developper workshop, Liège, Belgium, April 29, 2015 12 of 15
 Conclusion

• Effective masses important for material design

• Not much effort to ➚ precision
• Here
• DFPT implemented
• One less convergence to do
• Better numerical precision (& faster)
• Degenerate bands: accurate treatment, M −1
nn' → M n (θ , φ ) → σ n → M eqv
n

• Future directions
• electron-electron interactions
• electron-phonon interactions
• See: tests/v7/Input/t80.in

Abinit Developper workshop, Liège, Belgium, April 29, 2015 13 of 15

 Acknowledgments
Xavier Gonze’s group Thank you!

Samuel Poncé
Yannick Gillet
Michiel van Setten
CISM
Matteo Giantomassi
Yongchao Jia

Abinit Developper workshop, Liège, Belgium, April 29, 2015 14 of 15

 Performance
• Provided ground state calculation available
• Finite differences:
• 10 k-point X 4 bands X Solution of Ĥ ψ n = ε n ψ n
• DFPT:
• 1 k-point X 1 band X 3 directions X Solution of
13x
( )
P̂c Ĥ − ε n P̂c ψ α
n
α
= − P̂c Ĥ ψ n

CPU time (s)


Ge, 1st band, Γ
E Finite DFPT Ratio
20 4.0 0.35 11
50 17.6 1.35 13
Abinit Developper workshop, Liège, Belgium, April 29, 2015 15 of 15
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