The Plane-Wave Pseudopotential Method

CECAM Tutorial on Simulating Matter at the Nanoscale..., 13 Nov. 2006

Outline

Solution of the DFT problem: Self-consistency, global minimization

Crystals: periodicity, direct and reciprocal lattice, unit cell, Brillouin Zone
Plane waves (PW) basis set
Pseudopotentials (PP)
PW+PP technicalities

How to find the DFT ground state of a system ?

Solving the Kohn-Sham equations self-consistently
(T + V + VH (n) + Vxc(n))i = ii
with charge density n(r) =

fi|i(r)|2, i = combined k and band index,

fi = occupancy of states, and orthonormality constraints
i|j  = ij

By constrained minimization of the energy functional
E[{i}] =

fi
i|T + V |i + EH + Exc(n) + Eionion

with charge density and orthonormality constraints as above, i.e. minimize:

 i}, {ij }] = E[{i}] ij (
i|j  ij )
E[{
where the ij are Lagrange multipliers

Self-consistency
Starting from some guess of the input charge density nin(r):
in

in

out

(VH + Vxc)(n ) i(r) n

(r) =

fii(r)i(r)

Simply re-inserting nout as nin will almost invariably not converge. Reason: In
order to converge, such procedure must reduce the error at each step, but the
low-frequency (small-G) components of the error will likely not be reduced in typical
condensed-matter systems.
Simple mixing algorithm:
nnew = nout + (1 )nin,

0<<1

Guaranteed to converge if is small enough. More sophisticated algorithms (Anderson,

Broyden) use the input and output of several preceding steps to determine the next
optimal input combination.

Exchange-correlation potential
The exchange-correlation potential and energy in LDA are relatively simple functions
of the local charge density at point r:

Vxc(r) = vxc(n(r)),

Exc[n] =

exc(n(r))n(r)dr

They are easily calculated in r-space. Gradient-corrected functionals depend on the

gradient of the charge density as well. Slightly more complex to calculate.

Diagonalization of the Kohn-Sham Hamiltonian

Whatever approach one chooses, the basic building block of a DFT calculation is the
evaluation of the Kohn-Sham Hamiltonian HKS . How to solve H =  ? Expand
in some suitable basis set {i} as
(r) =

cii(r).

For an orthonormal basis set, solve

(Hij ij )cj = 0
j

where the matrix elements Hij =
i|H|j . For a non-orthonormal basis set, solve:

(Hij Sij )cj

where Sij =
i|j  (overlap matrix).

Total energy
Once convergence is reached, the total energy of the system may be calculated:
E=

fi
i|T + V |i + EH + Exc[n] + Eionion

where
2

n(r)n(r)
e

drdr
EH =
2
|r r|

Exc[n] =
exc(n(r))n(r)dr


Eionion =

e2

Z Z
2 , | R R |

(the primed sum excludes terms with R R = 0)

Equivalent expression for the energy, using Kohn-Sham eigenvalues:

E=


fii EH +

(exc(n) Vxc(n))n(r)dr + Eionion

Forces, Structural Optimization, Dynamics etc

The total energy depends on atomic positions R into the unit cell and on the lattice.
Forces acting on atoms are the derivatives of the total energy wrt atomic positions:


E
V
F =
=
fi
i|
|i
R
R

i
The Hellmann-Feynman theorem holds in DFT due to its variational character!
Once forces are calculated, one can perform structural optimization, molecular
dynamics, etc.

Periodicity
Let us consider the case of the infinite perfect crystals, having translation symmetry.
A perfect crystal is described in terms of
a unit cell that is periodically repeated
a basis of atomic positions di in the unit cell
a lattice of translation vectors R = n1R1 + n2R2 + n3R3
a reciprocal lattice of vectors G such that G R = 2l, with l integer.
Such conditions hold if G = m1G1 + m2G2 + m3G3 with Gi Rj = 2ij .

Non periodic systems ?

What about e.g. defects in crystals, surfaces, alloys, amorphous materials, liquids,
molecules, clusters? none of these has perfect periodicity. One can use supercells,
introducing an articial periodicity.
The supercell geometry is dictated by the type of system under investigation:
Molecules, clusters:
the supercell must allow a minimum distance of at least a few A ( 6) between
the closest atoms in dierent periodic replica.

 Defects in crystals:
the supercell is commensurate with the perfect crystal cell. The distance between
periodic replica of the defect must be big enough to minimize spurious defectdefect interactions.
Surfaces:
slab geometry. The number of layers of the materials must be big enough to
have bulk behaviour in the furthest layer from the surface. The number of
empty layers must be big enough to have minimal interactions between layers in
dierent regions.
Alloys, amorphous materials, liquids:
the supercell must be big enough to give a reasonable description of physical
properties.

Band Structure
The one-electron states (r) of a perfect crystal Hamiltonian H = T +V are described
by a band index i and a wave vector k.
It is convenient to consider the thermodynamic limit: a slab of crystal composed of
N = N1N2N3 unit cells, N , obeying Periodic Boundary Conditions:
(r + N1R1) = (r + N2R2) = (r + N3R3) = (r).
There are N wave vectors k in the unit cell of the reciprocal lattice, called the
Brillouin Zone. The one-electron states (energy bands) can be written as
i,k(r) = eikrui,k(r)
where ui,k(r) is translationally invariant:
ui,k(r + R) = ui,k(r).

Most popular basis sets:

Localized basis sets:

Bloch sums k = R exp(ik R)(r R) of functions centered on atoms
Linear Combinations of Atomic Orbitals (LCAO)
Gaussian-type Orbitals (GTO)
Linearized Mun-Tin Orbitals (LMTO)
Delocalized basis sets:
Plane Waves (PW)
Mixed basis sets:
Linearized Augmented Plane Waves (LAPW)
Projector Augmented Plane Waves (PAW)

PW basis set
A PW basis set for states of wave vector k is dened as
1
ei(k+G)r,

r|k + G =
N

2
h
|k + G|2 Ecut
2m

= unit cell volume, N = crystal volume, Ecut = cuto on the kinetic energy of
PWs (in order to have a nite number of PWs!). The PW basis set is complete for
Ecut and orthonormal:
k + G|k + G = GG
The components on a PW basis set are the Fourier transform:
|i =

ci,k+G|k + G

ci,k+G =
k + G|i =

1
N

i(r)ei(k+G)rdr = i(k + G).

Hamiltonian diagonalization
The solution of HKS i = ii at xed potential:



HKS (k + G, k + G ) iG,G ci,k+G = 0

G

requires the diagonalization of the matrix HKS , whose matrix elements are:
HKS (k + G, k + G) =
k + G|HKS |k + G

Matrix element of the Hamiltonian in PWs

Kinetic energy term:
2

h
(k + G)2GG

k + G|T |k + G =
2m

Hartree and exchange correlation terms:


n(G

G
)


2

k + G|VH |k + G  = VH (G G ) = 4e
|G G|2

and

k + G|Vxc|k + G = Vxc(G G)

where
f (G) =
is the Fourier Transform of f (r).

f (r)eiGrdr

(G = G!)

 External ionic potential:

V V (r) =

V(r d R)

cell R

1
i(k+G)r
i(k+G)r
e
V (r d R)e
dr

k + G|V |k + G  =
N

R


S(G G)V(G G)
=


where S(G) is the structure factor, containing geometrical information:

S(G) =

type

eiGdi

di cell

If the potential has spherical symmetry, V (r) = V (r), then:


4
sin(Gr)
2
V (G) = V (G) =
r V (r)
dr.

Advantages and disadvantages of various basis sets

Localized basis sets:
+ fast convergence with respect to basis set size (just a few functions per atom
needed)
+ no problem with nite systems
dicult to evaluate convergence quality (no systematic way to improve
convergence)
dicult to use (two- and three-center integrals)
dicult to calculate forces (Pulay forces)
Plane Waves:
slow convergence with respect to basis set size (many more PWs than localized
functions needed)
require supercells with nite systems
+ easy to evaluate convergence quality (just increase cuto)
+ easy to use (Fourier transform)
+ easy to calculate forces (no Pulay forces)

Charge density
The calculation of the charge density
n(r) =

fi,ki, k(r)i,k(r)

i,k

requires in principle a sum over an innite (N ) number of k-points in the Brillouin

Zone. As a matter of fact, for insulators just a few special points (i.e. a uniform
grid in most cases) are required. For metals, a much denser grid is usually required.
Charge density in reciprocal space:
1
n(G) =

iGr

n(r)e

dr =

G

fi,kci,k+G ci,k+G+G

i,k

This is NOT how n(G) is calculated, in practical calculations

The need for Pseudopotentials

Are PWs a practical basis set for electronic structure calculations? Not really! From
elementary Fourier analysis: length scale Fourier components up to q 2/.
In a solid, this means 4(2/)3/3BZ PWs (BZ = volume of the Brillouin
Zone).
C 1s2 2s2 2p2
2
1s
2s
2p
1
R(r)

Estimate for diamond: 1s wavefunction has

0.1 a.u., = (2)3/(a30/4) with lattice parameter

a0 = 6.74 a.u. 250, 000 PWs!

0.5

1.5

2
2.5
r (a.u.)

3.5

Need to:
get rid of core states
get rid of orthogonality wiggles close to the nucleus
Solution: Pseudopotentials (PP). A smooth eective potential that reproduces the
eect of the nucleus plus core electrons on valence electrons.