First principles calculations within DFT

some practical concerns

Ling-Ti Kong (š-N)

EMail: konglt@sjtu.edu.cn

School of Materials Science and Engineering, Shanghai Jiao Tong University

Dec 11, 2019

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Outline

1 k-sampling

2 Plane wave cutoff

3 Pseudo-potential

4 Born-von Karman PBC: look back

5 Summary: PP+PW within DFT

6 Further readings

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Kohn-Sham Equation for crystals
Schrödinger Equation ⇒ Eigen problem
X  ~2 |k + Gm |2 
δm,m0 + vm−m0 ci,m = i ci,m0
m
2me

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Brillouin zone integration

Properties like the electron density, total energy, etc., can be evaluated by integration over the
first Brillouin zone.
Electron density

occ. Z
1 X
n(r) = ni,k (r)dk, ni,k (r) = |ψi,k (r)|2
ΩFBZ FBZ
i
1 XZ
= fi,k · ni,k (r)dk
ΩFBZ FBZ
i
1 XX
= fi,k · ni,k (r)
Nk
k i

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k-point sampling: uniform vs non-uniform
Moreno and Soler (Phys. Rev. B 45(24):13891, 1992):
A mesh with uniformly distributed k-points is preferred.

Example: A rectangular lattice

(a) isotropic sampling
(b) finer sampling vertically
poor sampling horizontally

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Monkhorst-Pack scheme
Monkhorst & Pack (Phys. Rev. B 13:5188, 1976.):
3
X 2ni − Ni − 1
k= bi , ni = 1, · · · , Ni
2Ni
i=1

Example: 4 × 4 × 1 MP mesh for 2D square lattice

3 3 3 1
k1,1 = (− , − ) k1,3 = (− , )
8 8 8 8
3 1 3 3
k1,2 = (− , − ) k1,4 = (− , )
8 8 8 8

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Shifted Monkhorst-Pack mesh

Centered around Γ
Centered on Γ

25 k-points Shifted by (1/8, 1/8, 0)

16 k-points
Yet the same k-point density. 7 / 21
Symmetry on k in the first Brillouin zone

ψk+G = ψk ⇒ Limit k in FBZ.

~2
 
− 52 +veff (r) uk (r)e ikr = uk (r)e ikr
2me
~2
 
− 5 +veff (r) uk∗ (r)e −ikr = uk∗ (r)e −ikr
2
Congugate
2me
~2
 
2 ∗ ∗
− 5 +veff (r) u−k (r)e ikr = u−k (r)e ikr replace k by -k
2me

∗
u−k = uk ⇒ u−k = uk∗
 ∗
ψ−k = u−k e −ikr = uk e ikr = ψk∗
−k = k
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Symmetry on k in the first Brillouin zone

Ŝψik (r) = ψik (Ŝr)

= uik (Ŝr)e i S̆k·Ŝr
0
= uik (r)e ik r

ψk (r ) is a solution at k =⇒ ψ(Ŝr ) is a
solution at S̆k, with same energy/density.
X X
n(r) = ωk fi,k · ni,k (r)
k i

k ∈ irreducible Brillouin zone

# of sym. connected k
ωk =
total # of k in FBZ
Ŝψik (r) = ψik (Ŝr)
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Irreducible Brillouin zone

Example:
MP-mesh for 2D square lattice
4 × 4 × 1 MP mesh = 16 k-points in the FBZ.
4 equivalent k4,4 = ( 38 , 38 ) ⇒ w1 = 0.25
4 equivalent k3,3 = ( 18 , 38 ) ⇒ w2 = 0.25
8 equivalent k4,3 = ( 38 , 18 ) ⇒ w3 = 0.50
Brillouin zone integration

occ. occ. occ.

1X 1X 1X
n(r ) = ni,k4,4 + ni,k3,3 + ni,k4,3
4 4 2
i i i

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Irreducible Brillouin zone
Symmetry break: Hexagonal cell

Even meshes break the symmetry,

while meshes centered on Γ preserves
it. Shift the k-point mesh to preserve
hexagonal symmetry!

k-sampling: rules of thumb

bi
Keep density of k constant in each direction: Ni = const.
Denser k ⇒ more precise results.
NkIBZ does not necessarily scale with N. Symmetry matters
No k sampling needed for atoms or molecules!
Generally need to do convergence test!
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Smearing method: fractional occupation numbers
 
Fermi level F : the energy of the highest occupied band.
 

IBZ integration over the filled states: Occupation number


1 x ≤0
fi,k = Θ(ik − F ), Θ(x) =
0 x >0

For insulators and semiconductors, DOS goes to zero smoothly at the gap.
For metals, the resolution of the step function at F is very sensitive. 12 / 21
Smearing method: fractional occupation numbers
Trick is to replace sharp step function with a smoother function allowing partial occupancies at
the Fermi level.
Fermi-Dirac smearing
1 ik − F
fik = , x= , σ = kB T
1 + exp(x) σ
 Rx 
2
Gaussian smearing erf(x) = √2 e t dt
π 0


1
fik = [1 − erf(x)], σ has no physical meaning.
2

Methfessel-Paxton smearing
N Z x
−x 2
X
δ(x) ' DN (x) = An H2n e ; fik ' SN = 1 − DN (τ )dτ
n −∞
erf: error function, see http://en.wikipedia.org/wiki/Error function; 13 / 21
Cutoff: finite basis set

Computationally, a complete expansion in terms of infinitely many plane waves is not possible.
2 2
The coefficients, ci,m (k) decrease rapidly with increasing PW kinetic energy ~ |k+G
2m
m|
.

A cutoff energy value, Ecut , determines the

number of PWs (Npw ) in the expansion,
satisfying,

~2 |k + Gm |2
< Ecut
2m

Npw is a discontinuous function of the PW kinetic energy cutoff, while depends only on the
computational cell size and the cutoff energy value.

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Pseudopotential: why?
Reduction of basis set size
effective speedup of calculation
Reduction of number of electrons
reduces the number of d.o.f.
Unnecessary
Why bother? They are inert anyway· · ·
Inclusion of relativistic effects
relativistic effects can be included partially

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Pseudopotential: how?
Pseudopotential (PP)
A smooth effective potential that reproduces the effect of the nucleus plus core electrons on
valence electrons.

Norm conserving PP;

Ultrasoft PP;
Projector Augmented Wave PP;
··· 16 / 21
Born-von Karman PBC: always a necessity?
Supercell approach

point defect free surface single molecule

Supercell must be sufficiently large to maintain isolation.
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DFT: Ability and disability

Fundamentally, DFT can only predict the ground state electronic density and the ground state
total energy of a set of electrons under an external potential.
DFT can predict DFT cannot predict
Total energy Excited state energies
Forces Band gap
Lattice constants Band structures
Bond lengths Wave functions
Vibrational frequencies Fermi surface
Phonon frequencies Superconductivity
Electron density Excitons
Static dielectric response Electronic transport

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Accuracy

Accuracies can be expected

bond length ∼ 3% too small
bulk modulus ∼ 10% too high
phonon frequency ∼ 10% too high
energy difference > 1 mHartree
cohesive energy very poor (much too high)

Accuracies for properties that DFT technically does not predict

band gap 50% too small
band structure qualitatively reasonable
fermi surface qualitatively reasonable

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Influencing factors

Born-Oppenheimer approximation;
Density functional theory
LDA, GGA
LSDA
Pseudopotential
Kinetic energy cutoff
k-sampling
convergence criterion
···

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References and further readings

1 http://www.fhi-berlin.mpg.de/th/Meetings/FHImd2001/pehlke1.pdf
2 http://itp.tugraz.at/LV/ewald/TFKP/Literatur Pseudopotentiale/Roundy 05 DFT+PPsumm.pdf

3 http://www.phys.sinica.edu.tw/TIGP-NANO/Course/2007 Spring/Class%20Notes/CMS.20070531.pseudo.pdf

4 J. Singleton, Band theory and electronic properties of solids, Oxford University press.
5 http://cms.mpi.univie.ac.at/vasp/
6 http://www.quantum-espresso.org/
7 http://www.abinit.org/
8 http://www.cpmd.org/
9 http://www.icmab.es/siesta/

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