Pseudopotentials

Pseudopotentials
Electrons in molecules and solids

Core electrons
Valence electrons

Pseudopotentials
Some dificulties

Number of electrons
Core states oscilations

Pseudopotentials
Initial idea of pseudopotential

Let |C , Ki be a core state with k-vector K within the BZ, and

|K + Gi a plane wave.

Pseudopotentials
Initial idea of pseudopotential

Let |C , Ki be a core state with k-vector K within the BZ, and

|K + Gi a plane wave.
We define the state |K + GiOPW as
X
|K + GiOPW = |K + Gi + AC ,K |C , Ki (1)
C

Pseudopotentials
Initial idea of pseudopotential

Let |C , Ki be a core state with k-vector K within the BZ, and

|K + Gi a plane wave.
We define the state |K + GiOPW as
X
|K + GiOPW = |K + Gi + AC ,K |C , Ki (1)
C

such that
hC , K|K + GiOPW = 0 (2)
for every C .

Pseudopotentials
Initial idea of pseudopotential

Let |C , Ki be a core state with k-vector K within the BZ, and

|K + Gi a plane wave.
We define the state |K + GiOPW as
X
|K + GiOPW = |K + Gi + AC ,K |C , Ki (1)
C

such that
hC , K|K + GiOPW = 0 (2)
for every C .
As a result

AC ,K = −hC , K|K + Gi (3)

Pseudopotentials
Initial idea of pseudopotential

If we use these OPW functions as basis for the valence states, we

have
X
|V , Ki = BVK,G |K + GiOPW
G
X X X
= BVK,G |K + Gi − BVK,G hC , K|K + Gi|C , Ki
G G C
= |V , KiPW + |V , Kicore (4)

Pseudopotentials
Initial idea of pseudopotential
Substituting on SE:

Ĥ|V , Ki = EVK |V , Ki (5)

Pseudopotentials
Initial idea of pseudopotential
Substituting on SE:

Ĥ|V , Ki = EVK |V , Ki (5)

X X
Ĥ|V , KiPW − Ĥ BVK,G hC , K|K + Gi|C , Ki =
G C
X X
EVK |V , KiPW − EVK BVK,G hC , K|K + Gi|C , Ki (6)
G C

Pseudopotentials
Initial idea of pseudopotential
Substituting on SE:

Ĥ|V , Ki = EVK |V , Ki (5)

X X
Ĥ|V , KiPW − Ĥ BVK,G hC , K|K + Gi|C , Ki =
G C
X X
EVK |V , KiPW − EVK BVK,G hC , K|K + Gi|C , Ki (6)
G C

X X
Ĥ|V , KiPW − BVK,G ECK hC , K|K + Gi|C , Ki =
G C
X X
EVK |V , KiPW − EVK BVK,G hC , K|K + Gi|C , Ki (7)
G C

Pseudopotentials
Initial idea of pseudopotential

Ĥ|V , KiPW + V̂ 0 |V , KiPW = EVK |V , KiPW (8)

Pseudopotentials
Initial idea of pseudopotential

Ĥ|V , KiPW + V̂ 0 |V , KiPW = EVK |V , KiPW (8)

where

X X
V̂ 0 |V , KiPW = BVK,G (EVK − ECK )hC , K|K + Gi|C , Ki (9)
G C

Pseudopotentials
Initial idea of pseudopotential

Ĥ|V , KiPW + V̂ 0 |V , KiPW = EVK |V , KiPW (8)

where

X X
V̂ 0 |V , KiPW = BVK,G (EVK − ECK )hC , K|K + Gi|C , Ki (9)
G C

X X
V̂ 0 |V , KiPW = (EVK − ECK ) BVK,G hC , K|K + Gi|C , Ki (10)
C G

Pseudopotentials
Initial idea of pseudopotential

Ĥ|V , KiPW + V̂ 0 |V , KiPW = EVK |V , KiPW (8)

where

X X
V̂ 0 |V , KiPW = BVK,G (EVK − ECK )hC , K|K + Gi|C , Ki (9)
G C

X X
V̂ 0 |V , KiPW = (EVK − ECK ) BVK,G hC , K|K + Gi|C , Ki (10)
C G

X
V̂ 0 |V , KiPW = (EVK − ECK )hC , K|V , KiPW |C , Ki (11)
C

Pseudopotentials
General form

In general we can define

X
V̂ 0 |αi = hFC |αi|C i (12)
C

With FC = hr|FC i being arbitrary functions.

Pseudopotentials
General form

In general we can define

X
V̂ 0 |αi = hFC |αi|C i (12)
C

With FC = hr|FC i being arbitrary functions.

B. J. Austin, V. Heine, L. J. Sham, Phys. Rev. 127, 276 (1962).

Pseudopotentials
General form

We can use perturbation theory for Ĥ 0 = Ĥ + V̂ 0 to show that if

Ĥ|C i = EC |C i and Ĥ|V i = EV |V i (13)

then

Ĥ 0 |C i0 = EC0 |C i0 and Ĥ 0 |V i0 = EV0 |V i0 (14)

with

EC0 6= EC and EV0 = EV (15)

and
X X
|C i0 = AC ,C 0 |C 0 i and |V i0 = |V i + BV ,C 0 |C 0 i (16)
C0 C0

Pseudopotentials
General form

In summary
New core energy eigenvalues 6= old core energy eigenvalues
New core states → linear combination of old core states
New valence energy eigenvalues = old valence energy
eigenvalues
New valence states → the corresponding old valence state
plus a linear combination of old core states

Pseudopotentials
General form

In summary
We should look to FC so as to have smooth valence states.
Possible strategy: norm-conserving pseudopotentials.

Pseudopotentials
Norm-conserving Pseudopotentials

Norm-conserving pseudopotentials are those obeying the following

rules:
Real and pseudo valence eigenvalues are equal for a given
atomic configuration;
Real and pseudo valence eigenfunctions are equal beyond a
given cutoff radius rc ;
Real and pseudo valence electronic densities integrated from 0
to rc are the same;
Real and pseudo valence eigenfunctions have the same
logaritmic derivative (and its first derivative on energy)
beyond the cutoff radius rc ;
D. R. Hamann, M Schluter, C Chiang, Phys. Rev. Lett. 43, 1494
(1979).

Pseudopotentials
Non-singular pseudopotentials

Kerker proposed a class of pseudopotentials by the following

requirements
Real and pseudo valence eigenvalues are equal;
Pseudo valence eigenfunctions have no nodes and are equal to
the actual eigenfunctions for r > rc ;
1st and 2nd radial derivatives of the real and pseudo valence
eigenfunctions are equal for r > rc ;
Real and pseudo charges coincide for r < rc ;
G. P. Kerker, J. Phys. C 13, L189 (1980).

Pseudopotentials
Non-singular pseudopotentials

In this procedure, we impose a chosen form for the radial pseudo

eigenfunction:

RlPS (r ) = r l f (r ), for r < rc (17)

RlPS (r ) = Rl (r ), for r > rc (18)

with

f (r ) = exp[p(r )]; p(r ) = αr 4 + βr 3 + γr 2 + θr + δ (19)

Pseudopotentials
Non-singular pseudopotentials

By inversion of SE, we can show:

2(l + 1) 0
VlPS = E + p 00 + p 02 + p (20)
r
so that we make θ = 0 to avoid singularities in the origin.

Pseudopotentials
Non-singular pseudopotentials

Condition 2 gives
" #
Rl (rc )
p(rc ) = ln (21)
rcl+1

Pseudopotentials
Non-singular pseudopotentials

Condition 2 gives
" #
Rl (rc )
p(rc ) = ln (21)
rcl+1

Condition 3 gives

Rl0 (rc )
rc = 1 + l + rc p 0 (rc ) (22)
Rl (rc )

Pseudopotentials
Non-singular pseudopotentials

Using the continuity of the pseudopotential, one can show

Rl2 (rc )
rc2 V (rc ) + (l + 1)2 − rc2 (E + 2(l+1)
) = rc2 p 00 (rc ) (23)
rc

Pseudopotentials
Non-singular pseudopotentials

Using the continuity of the pseudopotential, one can show

Rl2 (rc )
rc2 V (rc ) + (l + 1)2 − rc2 (E + 2(l+1)
) = rc2 p 00 (rc ) (23)
rc

With these last three equations, we can put α, β and γ as

functions of δ and use the condition 4 to obtain a transcedental
equation for δ.

Pseudopotentials
Troullier-Martins

Conditions
Norm conservation
Continuity of the first four derivatives of the valence pseudo
eigenfunctions for rc
Null curvature of the pseudopotential at the origin

Pseudopotentials
Troullier-Martins

Advantages
Longer cutoff radii
Faster convergence
N. Troullier, J. L. Martins, Phys. Rev. B 43, 1993 (1991).

Pseudopotentials