Summer School on First Principles Calculations for Condensed Matter and Nanoscience

August 21 – September 3, 2005

University of California
Santa Barbara, California

PROJECTOR AUGMENTED-WAVE (PAW) BASICS

F. Jollet, M. Torrent

Commissariat à l'Energie Atomique

Centre d’Etudes de Bruyères le Châtel
France

PAW basics 29/08/2005 1

Summary

PAW basics 29/08/2005 2

Historical context

! " #$
% & $
'
&

(
)*)+(),-. / !/ 0 0 1 "
(
),-. 2/!2 0/ "
(
))3. 4'!4 0' "
(
))(. !5 "
(
))6. 7 !/ "

PAW basics 29/08/2005 3

Historical context
Wavefunctions are developped on a basis which is…

Localized Delocalized

Plane waves
Spherical harmonics + special functions

All electrons are taken into account Only valence electrons are taken into account

Pseudopotentials

Pb: - The atomic basis is Pb: - Use of pseudos wavefunctions

moving with atoms - Big size of the plane wave basis

« The Projector Augmented-Wave method is an extension of augmented

PAW wave methods and the pseudopotential approach, which combine their
traditions into a unified electronic structure method »
Peter Blöchl

PAW basics 29/08/2005 4

References

Projector augmented wave method », P. Blöchl, Phys. Rev. B 50, 17953 (1994) [Ref 1]

« Comparison of the projector augmented-wave, pseudopotential, and linearized

augmented-wave plane-wave formalisms for density-functional calculations of solids », N.
Holzwarth et al., Phys. Rev. B 55, 2005 (1997) [Ref 2]

« From ultrasoft pseudopotentials to the projector augmented-wave method », G. Kresse

and D. Joubert, Phys. Rev. B 59, 1758 (1999) [Ref 3]

PAW basics 29/08/2005 5

A linear transformation I

% & τ .

~
Ψn = τ Ψn 8

PAW basics 29/08/2005 6

A linear transformation II

8 +
& .
τ = 1+ SR
R

9 0 φi 0

~
: 0 φi 0
φi $

~ ~
φi = φi + φi − φi .
~ ~
S R φi = φi − φi

PAW basics 29/08/2005 7

A linear transformation III

9 0 .
~
ψ~n = φi ⋅ ci
i

~ ~
9 ~
pi 0 ; 0 pi φ j = δ i , j
0 .
~ ~
ψ~n = φi ~pi Ψn
i

S R ψ~n =
~
S R φi ~
~
pi Ψn = ( φ~
i − φi ) ~p
i
~
Ψn
i i

~
Ψ n = Ψn + (φ i
~
− φi ) ~p i
~
Ψn
i

PAW basics 29/08/2005 8

The PAW method
.
n = ~n + (φ i − φi
~
) ~p i
~
n =τ ~n (1)
i

Plane wave part All electron spherical part Pseudized spherical part

~ ~
% . A = f n Ψn A Ψn = f n Ψn τ * Aτ Ψ n
n n

< . .

n(r ) = n~ (r ) +
R
(n 1
R (r ) − n~R1 (r ) ) ~
E = E+ ( ~1
E − ER
1
R )
R

PAW basics 29/08/2005 9

Notations

;
#

:
: =

~
E = E+ ( ~1
E − ER
1
R )
R

PAW basics 29/08/2005 10

Calculation of the energy I
9 0 r r .

n(r ) = n~ (r ) + (n 1
R (r ) − n~R1 (r ) ) (2)
R

n~ (r ) = f n ψ~n r r ψ~n
n

n1R (r ) = ρ ijR φi r r φ j
i, j

~ ~
n~R1 (r ) = ρ ijR φi r r φ j
i, j

ρ ijR = f n ψ~n ~ p j ψ~n

pi ~
n

' . E = T + EHartree + E xc
> 0 ψ~n

PAW basics 29/08/2005 11

Calculation of the energy II

! ? @A
".

nT = n + nZc = (n~ + nˆ + n~Zc ) + (n1 + nZc ) − (n~1 + nˆ + n~Zc )

n~T nT1 n~T1

' nˆ (r )
.

(n1 (r ) − n~1 (r ) − nˆ (r )) ⋅ r − R ⋅ Ylm* (r − R ) ⋅ dr = 0

l

0 n1R − n~R1 − nˆ R
# B$
M lmYlm (rˆ)
V (r ) = 4π
lm (2l + 1)r l +1

PAW basics 29/08/2005 12

Calculation of the energy III

E Hartree =
1
2
nT (r )nT (r ' )
r − r'
1
2
1
2
( ) 1
( )(
drdr ' = (nT )(nT ) = (n~T )(n~T ) + nT1 − n~T1 (n~T ) + nT1 − n~T1 nT1 − n~T1
2
)
(1) (2) (3)

9 (
0 nT1 − n~T1 )
In (2), n~T is replaced by n~T1

9 .

EHartree = EH [n~ + nˆ ] + vH [n~Zc ][n~ + nˆ ]dr + U (R , Z ion )

[ ] [ ] [ ] [
+ EH n1 + vH [nZc ] n1 dr − EH n~1 + nˆ − vH [n~Zc ] n~1 + nˆ dr ]
R R

PAW basics 29/08/2005 13

Calculation of the energy IV

~
E = E+ ( ~1
E − ER
1
R )
R

~ ~ ∆ ~
E= f n Ψn − Ψn + E xc [n~ + nˆ + n~c ] + EH [n~ + nˆ ] + vH [n~Zc ][n~ + nˆ ]dr + U (R, Z ion )
n 2
~
ER1 = ρijR φi
~ −∆ ~
2
[ ] [ ] [ ][
φi + E xc n~R1 + nˆ R + n~cR + EH n~R1 + nˆ R + vH n~ZcR n~R1 + nˆ R dr ]
ij R

φi + E xc [n1R + ncR ]+ EH [n1R ]+ vH [n~ZcR ][n1R ]dr

− ∆
ER1 = ρ ijR φi
ij 2 R

PAW basics 29/08/2005 14

Calculation of the energy V
!

9 0 . nˆ (r ) = ρ ij QijL (r )
( i , j ), L

QijL (r ) = qijL g l ( r − R )YL (r − R )

[ ~ ~
] l
qijL = φi* (r )φ j (r ) − φi * (r )φ j (r ) r − R YL* (r − R )dr
R
g l (r ) r l r 2 dr = 1
R

' vH [n~Zc ] $
' ?B @A 2 C $

9 / ?B (
A0 .

vH [n~Zc ] = v + vH (nZc
K
)
g (r )
n~ZcK = 0 (nc − n~c )dr − Z ion + n~c
4π R

v # /

PAW basics 29/08/2005 15

Calculation of the Hamiltonian I

' . Ψn Ψm = δ nm
~ ~
. Ψn S Ψm = δ nm

S = 1+ ~
piR (φ i
R ~ ~
φ jR − φi R φ jR ) ~p R
j
R ,ij

~~ ~
. H n = εnS n

~ dE 1
H = ~ = − ∆ + v~eff + ~
pi Dij ~
pj
dn 2 i, j

PAW basics 29/08/2005 16

Calculation of the Hamiltonian II

~ dE 1
H = ~ = − ∆ + v~eff + ~
pi Dij ~
pj
dn 2 i, j

v~eff = vH [n~ + nˆ + n~Zc ] + vxc [n~ + nˆ + n~c ]

Dij = v~eff (r )QijL (r )dr

L

+ φi −
∆
2
[ ]
+ vH n1 + nZc + v xc n1 + nc φ j[ ]
~ ∆
[ ] [ ~
− φi − + vH n~1 + nˆ + n~Zc + v xc n~1 + nˆ + n~c φ j −
2
] v~eff1 (r )Qˆ ijL (r )dr
L

! .

Dij = Dij0 + ρ kl Eijkl + Dijxc + v~eff (r )Qˆ ijL (r )dr

kl L

PAW basics 29/08/2005 17

The PAW method - overview

"## $ %
&"'%
$()
: #
'
'

"*+"('",-)
'
7 +
! + "
' 7 $
$
9 "
7 $

PAW basics 29/08/2005 18

 The PAW method – atomic data

9 7 0 .

&

{φ }, {φ }, {~p },
i
R ~R
i i
R
VH [n~Zc ], nc , n~c

~ Pseudized
All electron partial waves Projectors (dual of
~
φ
i

φi R) Core density core density

Pseudized soft partial waves Hartree potential due to nuclueus
and core electrons (local pot.)

# $%

PAW basics 29/08/2005 19

Approximations: ultrasoft and norm-conserving
~ dE 1
H = ~ = − ∆ + v~eff + ~
pi Dij ~
pj
dn 2 i, j

Dij = Dij0 + ρ kl Eijkl + Dijxc + v~eff (r )Qˆ ijL (r )dr

kl L

(" & $%
D ρ
.

Dij = Dij0,US + v~eff (r )Qˆ iL, j (r )dr '

L

)" & $% "

Qˆ iL, j (r ) = 0 Dij = Dij0, KB * "

S=I

PAW basics 29/08/2005 20

Example of fcc Ca

. . ∆! "F(
8 + E
7 > 77 .
7 7 E . G63
7 +> 77 . -3
7 + 7 . -3

PAW-uspp

B .
E . +=(
3$@ $ $
7 +> 77. +=(
3$- $ $

PAW basics 29/08/2005 21

Example of fcc oxygen

. . ∆! "F(
8 + '
8 + '4 .
7 > 77 ' . @3
'4 . @@
7 +> 77 . (H

PAW-uspp

B .
' . + = H$*I $ $
,+ = -( 3E7
7 +> 77. +=H $,3 $ $
,+ = -3,E7

PAW basics 29/08/2005 22

Example of BaTiO3

. . ∆! "F(
8 + '
7 > 77 .
' . HI
7 +> 77 . -@

7> 7 +/J .
' . -$'= -I3 $
PAW-uspp 7 +> 77. -$'= (33 $

B .
' . += *$6H $ $
7 +> 77. +=* $6, $ $

PAW basics 29/08/2005 23

Conclusions

' 7 K L

0 0 0 7

D 7 M

PAW basics 29/08/2005 24