MAGNETISM IN DFT

FROM THEORY TO PRACTICE

(Paris, France)
Saclay

Cyrille Barreteau
CEA Saclay
(Copenhagen, Denmark)
Lyngby

2 JUILLET 2014

MASTANI, Pune, INDIA, July 2014 | PAGE 1

MAGNETISM
From the atomic nucleus to the inner core of Earth
time

Magnetic rotor

GMR Read Head

NMR
length

2 JUILLET 2014

MASTANI, Pune, INDIA, July 2014 | PAGE 2

MAGNETISM
Intense activity in which nanomagnetism plays a crucial role
Search for permanent hard magnets without rare earth
Replace Samarium-Cobalt, Neodyum by nanostructured cheap TM magnets
Spintronics

From Fundamentals to applications

micromagnetics

DFT is the perfect tool to adress (at least partly) most of these problems
MASTANI, Pune, INDIA, July 2014 | PAGE 3

DENSITY FUNCTIONAL THEORY

Hohenberg & Kohn (1964) + Kohn Sham (1965)

E n T0 n Vext (r )n(r )d 3r

n(r )n(r ') 3 3

d rd r ' EI I E xc n

2
r r'

2
Veff (r ) (r ) (r )

2m

H KS

VHartree (r )

Vext (r )

n(r ) , (r ) 2 (r )
2

occ

occ

if

Vext (r ) VHartree (r ) Vxc (r )

n(r ') 3
d r'
r r'

Vxc (r )

Exc
n(r )

(pseudo)-potental describing the interaction of valence electrons

with the ions (nucleus+core electrons)
Can also include a true external potential

2 JUILLET 2014

MASTANI, Pune, INDIA, July 2014 | PAGE 4

Local density approximation (LDA)

Exc n n(r ) xc (n(r ))d 3r

xc (n) : exchange correlation energy (per particle) of homogenous gas

xc (n) x (n) c (n)

3 3n

x ( n)
4
c ( n) F ( n)

1
3

Hartree Fock in an homogenous jellium

Parametrized from QMC

Vxc (r ) (n xc (n))
dn
nn (r )

2 JUILLET 2014

MASTANI, Pune, INDIA, July 2014 | PAGE 5

Generalized Gradient approximation (GGA)

Exc n n(r ) xc (n(r ), n(r))d 3r

Exc n n(r ) xchom (n(r )) Fxc (n(r ), n(r)) d 3r
xchom (n) : exchange correlation energy (per particle) of homogenous gas

Fxc (n(r ), n(r)) : dimensionless enhancement factor

Some important sum rules and other relevant conditions should be verified
But still a large variety of functionals
Perdew and Wang (PW91)
Most popular

Perdew Burke and Enzerhof (PBE)

2 JUILLET 2014

MASTANI, Pune, INDIA, July 2014 | PAGE 6

DFT implementation diagram

Initial guess

Kohn Sham algorithm

Combination of atomic densities

n(r )
Effective potential

Vext (r ) VHartree (r ) Vxc (r )

Solve Poisson equation
but not in Harris Functional scheme

Solve KS equation

V
(
r
)

(r ) (r )
eff
2m

charge mixing

Determine the Fermi level

electron density and total energy

n(r ) 2 (r )
occ

Etot n(r )

Converged?
2 JUILLET 2014

T Eband Edc

Analayse results
MASTANI, Pune, INDIA, July 2014 | PAGE 7

Spin polarization
Spin moment operator

s g s B

gs 2

0 i
0 1
y

i 0
1 0

(collinear case)

spin moment

zspin s , z B z
occ

1 0
z

0 1

0
or

in collinear case

spin
z

(r ) (r ) (r ) n n

occ

occ

Orbital polarization
orbital moment operator

L B

B l

orbital moment

m orb (r ) L
occ

Average orbital moment: usually small (quenched) in bulk

and strictly null if spin-orbit coupling (SOC) is ignored.
2 JUILLET 2014

MASTANI, Pune, INDIA, July 2014 | PAGE 8

Local Spin density approximation (LSDA)

xc (n , n ) x (n , n ) c ( n , n )

Alternative formulation

nn n

m n n

x (n, ) x (n, 0) x (n,1) x (n, 0) f x ( )

m
n

1 (1 ) 3 (1 ) 3 2 1 if 1
f x ( )

1
2
2 3 1
0 if 0
4

c (n, ) c (n, 0) c (n,1) c (n, 0) f c ( ) f c ( ) f x ( ) (Perdew Zunger)

Spin dependent potential

Veff Vext (r ) VHartree (r ) Vxc (n(r ), m(r )) Bxc (r )

(n(r ), m(r))
Vxc (r ) xc (n , n ) n(r ) xc

n(r )

(n(r), m(r))
Bxc (r ) n(r ) xc

m(r )

Bxc (r ) exchange correlation magnetic field

Bext (r ) external magnetic field can be added

2 JUILLET 2014

MASTANI, Pune, INDIA, July 2014 | PAGE 9

Spin polarized DFT implementation diagram

Initial guess

n (r ) (n(r ) m(r ))
1
2

Combination of atomic densities

+ initial moment (symmetry breaking)

Spin dependent potential

Vext (r ) VHartree (r ) Vxc (r )

Solve the two KS equation

2

V
(
r
)

(
r
)

(r )
eff
2m

charge mixing

Determine the common Fermi level

electron and spin density, total energy

2
n(r ) n (r ) n (r )

n (r ) (r )
Etot n(r ), m(r )

m(
r
)

n
(
r
)

n
(
r
)
occ
Converged?
2 JUILLET 2014

EF EF EF

Analayse results
MASTANI, Pune, INDIA, July 2014 | PAGE 10

ANALYSE RESULTS
What do we get out of spin-polarized DFT calculation
Pw(scf)
Pw(scf)

Etot neq , meq Total energy find most stable structure! (not always easy..)
Total (and absolute) spin magnetic moment

M abs n (r ) n (r ) d 3r

M n (r ) n (r ) d 3r

Pw(nscf)

Spin polarized band structure (for up and down spins)

Pw(scf)
+projwf.x
+pp;x

Local analysis (many options)

DOS

ni ( E )

at
i ,

n( E , r ) (r ) E
2

mi iat,
Local moment

occ

iat,

m(r ) (r ) (r )
2

2 JUILLET 2014

occ

Atomic moment
Spin density
MASTANI, Pune, INDIA, July 2014 | PAGE 11

PHYSICAL INSIGHT
DFT is a very powerful tool but there is still a need for simpler phenomenological
models and local analysis to get a deeper physical understanding of the phenomena

Stoner model
Heisenberg/Ising model
Local analysis

2 JUILLET 2014

mi

MASTANI, Pune, INDIA, July 2014 | PAGE 12

LSDA and the Stoner model

xc (n, ) xc (n, 0) 12 xc" (n, 0) 2 o( 2 )

Bxc (r )

1 "
xc (n(r ), 0)m(r )
n(r )

Veff V

n (E) n (E
0

0
eff

M : magnetic moment per atom

IM

1 xc" (n(r ), 0) 3
M m(r )d r I
d r0

n(r )
Rigid shift of up and down eigenvalues

IM )
N

E
EF

EF

IM

(n 0 ( E 12 IM ) n 0 ( E 12 IM )) dE EF ( M )

EF

0
0
1
(n
(
E

IM
)

n
( E 12 IM )) dE
2

F (M ) M
n ( E ) n 0 ( E
2 JUILLET 2014

IM )
MASTANI, Pune, INDIA, July 2014 | PAGE 13

Stoner criterion

Non zero solution if

F (M )

F '(0) 1

M max
M F (M )

M 0 M1

In0 ( EF ) 1

M max

1eV

In most elements

n0 ( EF )

plays a crucial role in magnetic

susceptibility and onset of magnetism

Criterion can be also derived by analyzing

0
M

H (1 In0 ( EF ))

magnetic susceptibility

Total energy

Etot 12 Imi2
occ

Nowadays Stoner model often used in parametrized Tight-Binding models

2 JUILLET 2014

H ij H ij0

IM i ij

MASTANI, Pune, INDIA, July 2014 | PAGE 14

General trends
Low coordination favors magnetism
n( E )

Z
W

n( EF )

Spin magnetic moment is generally enhanced on

low coordinated atoms

Z : number of neigbors

2 JUILLET 2014

MASTANI, Pune, INDIA, July 2014 | PAGE 15

General trends
Lattice expansion generally favors magnetism and vice versa
n( E )

q ( R / R0 ) 1

M (d )

Cr bcc

2 JUILLET 2014

E(d )
Pd fcc

Fe bcc

n( EF )

Pd fcc

Rh6

MASTANI, Pune, INDIA, July 2014 | PAGE 16

Multiple magnetic solutions

Stoner criterium does not tell the whole story
unstable

stable

stable

F ( M in ) M out
M in M out ?

The iterative scheme converges towards a solution which depends on initial spin moment
How to be sure not to miss the most stable solution?

Several starting magnetization

(fishing strategy)
Fix spin moment (FSM) calculation
allow to explore E(V,M) energy surface
2 JUILLET 2014

MASTANI, Pune, INDIA, July 2014 | PAGE 17

Fixed Spin moment

Conventional scheme
EF EF

N N N

FSM

M ini M

EF EF

N N N

M N N

many calculations

one scf loop

EF 0

M M ini

M
E

EF 2 H ( M )

Emin

EF 0

M M ini

Emin
2 JUILLET 2014

MASTANI, Pune, INDIA, July 2014 | PAGE 18

Penalization technique
Add a penalization term to the total energy functional to impose a given condition

DFT

E n, m Etot n, m (m(r ) m 0 (r )) 2 d 3r

Minimization modified KS Hamiltonian

H H 2 (m(r ) m0 (r )) .

TB

E ci Etot ci mi m0

ci iat
i

H ij H ij 2 (mi m 0 ). ij

2 JUILLET 2014

MASTANI, Pune, INDIA, July 2014 | PAGE 19

SOME IMPORTANT TECHNICAL POINTS

Before running (or trusting) a DFT calculation you should be aware of
several important technicalities
Pseudopotential (LDA pz /GGA pw91, pbe)
Energy cut-off (ecutwfc, ecutrho8ecutwfc for US pseudo)
K-points sampling: denser mesh for metals
note that in QE the #k points is doubled in spin-polarized system
Smearing (smearing, degausss) Marzari Vanderbilt recommended
Initial magnetization (starting_magnetization)
Number of computed eigenvalues (nbnd) often needs to be increased
Convergence threshold (conv_thr)

2 JUILLET 2014

MASTANI, Pune, INDIA, July 2014 | PAGE 20

pseudopotential
As a rule of thumb: aLDA <aexp<aGGA
LDA bad for 3d but OK for 5d problematic for alloys (FePt, CoPt)

E(V)

bcc FM

fcc NM
bcc FM

2 JUILLET 2014

hcp NM

MASTANI, Pune, INDIA, July 2014 | PAGE 21

Cr bcc AF

Initial magnetization
Define the system as simple cubic with 2 types of atoms
per unit cell and opposite starting magnetization

ibrav=1
nat=2

starting_magnetization(1)= 0.5
starting_magnetization(2)=-0.5

ntyp=2

m m0 cos(q.R )

Cr SDW

L 20a0 q (1

q 0.953 0.95 in unit of

2
a0

1 2
)
20 a0

| PAGE 22

2 JUILLET 2014
MASTANI, Pune, INDIA, July 2014

NON COLLINEAR MAGNETISM

Why should we care about non collinearity?

Mn

Non-collinearity does exist!

The future is in skyrmions

2 JUILLET 2014

Spin excitation

MASTANI, Pune, INDIA, July 2014 | PAGE 23

Spin gymnastics
( x, y, z ) global axis

"

sin cos

m m sin sin
cos

( x ", y ", z ") local axis

0

m" m 0
1

Spin rotation matrix

"

"

e i 2 cos( ) e i 2 sin( )
i 2 z i 2 y
2
2

U ( , )
e
e

i
i
e 2 sin( ) e 2 cos( )

2
2

i " U ( , ) iU ( , )
x , y , z also transforms like a space vector
2 JUILLET 2014

i " Rij j

MASTANI, Pune, INDIA, July 2014 | PAGE 24

2x2 matrices algebra

M M2( )

M aI b.

a 12 Tr (M )

b 12 Tr (M. )

If M is hermitian then a and b are real numbers

diagonalization

2 eigenvalues a b

b b n

sin cos

n sin sin
cos

a b
M U
0

U
a b
0

e i 2 cos( ) e i 2 sin( )
2
2

e i 2 sin( ) ei 2 cos( )

2
2

2 JUILLET 2014

MASTANI, Pune, INDIA, July 2014 | PAGE 25

From electron density/magnetization vector to the Density matrix

n, m
n(r ) f (r ) (r ) m(r ) f (r ) (r )

f ' (r )
' (r )

, , '

Density matrix

'

(r ) f

n,m

'

(r ) (r )

(r )

1
1 n mz
(r ) n(r ) I .m(r )
2
2 mx im y

mx im y

n mz

n,m

n Tr ()
2 JUILLET 2014

m Tr ( )
MASTANI, Pune, INDIA, July 2014 | PAGE 26

The non-collinear Stoner Hamiltonian

Local spin axis

"
Stoner

I 1 0
I
m
m z "
2 0 1
2

Global spin axis

H Stoner UH

I cos
U m i
2 e sin

"
Stoner

e i sin

cos

0 1
0 i
1 0
I
H Stoner m sin cos

sin

sin

cos

1
0
i
0
0

1
2

I
H Stoner m.
2
A lot of fuss for a straightforward result!
2 JUILLET 2014

MASTANI, Pune, INDIA, July 2014 | PAGE 27

Kohn Sham Hamiltonian

'

H KS

2m

2 Veff ' (r )

n(r ') 3
'
Veff (r ) Vext (r )
d r ' ' Vxc ' (r )
r r'

Exc ( r )
'

E (r )
n(r ') 3
Veff ' (r ) Vext (r )
d r ' xc
' .B xc
r

r
'

n
(
r
)

Exc ( r )
In LDA

m ( r )

xc (n) f (n)

xc (n )
0
diagonalization of diagonalization of xc ()

0
xc (n )

(m(r ), (r ), (r )) at each position r in space

rotate "back" with matrix U to get xc ((r ))

In GGA

xc (n) f (n, n)

Additional complication since

and cannot be diagonalized in the same basis

off diagonal terms of are neglected

2 JUILLET 2014

MASTANI, Pune, INDIA, July 2014| PAGE 28

PHYSICAL INSIGHT
Classical Heisenberg Hamiltonian

ej

1
E J ij ei e j
2 i, j
J ij

ei

Can be obtained by various approaches from DFT

(not yet available in QE)

J ij 0

J ij 0

Favors FM order

J ij

Favors AF order

Frustration
Fairly happy

2 JUILLET 2014

MASTANI, Pune, INDIA, July 2014 | PAGE 29

Some examples
Fe/Cr(001) interface

Cr/Cu(111)

Fe/Cr(110) interface

Fe

Cr
Fe bibyramidal cluster

Ecol Encol
2 JUILLET 2014

Ecol Encol
MASTANI, Pune, INDIA, July 2014| PAGE 30

SPIN-ORBIT COUPLING
Why should we care about SOC?
Small quantity (at least in 3d) with huge physical consequences

At the origin of magneto-crystalline anisotropy ..and therefore of the stability of magnets!

bccFe

E ,

hcpCo

fccNi

At the origin Anisotropic Magneto-Resistance

B
current
2 JUILLET 2014

MASTANI, Pune, INDIA, July 2014 | PAGE 31

Relativistic effects

Dirac equation

0 i
i

0
i

(r , t )
c.p mc 2 V (r , t )
t
1 (r , t )

I 0

(
r
,
t
)

(
r
,
t
)

(r , t )
0 I
3

(r , t )

Scalar relativistic

Small v/c limit (r , t )

H
2 V (r ) B (L 2S).B
2m

p4
3 2
8m c

1 1 dV
L.S (r )l.s 12 ( r )l.
2 2
2m c r dr

2
2 2

8m c

2 JUILLET 2014

2V

(r , t )

Large component

(r , t )

Small component

v
(r , t )
c

Schrdinger + Zeeman

Mass-velocity

Spin-Orbit Coupling

Contraction and stabilization

of s and p shells + expansion
and destabilization of d and f
Splitting of orbitals with
angular momentum.

Darwin
MASTANI, Pune, INDIA, July 2014| PAGE 32

The good basis

Without SOC

L et S commute with H
2

Basis diagonalizing

l, m

L , Lz ,S ,Sz
2

L l, m l(l 1)

l, m

Lz l, m m l, m

With SOC

3
4

Sz

L et S no longer commute with H H so

we consider

J LS

Basis diagonalizing

j, m j

J , Jz

J j, m j j(j 1)
J z j, m j m j

j, m J

j, m j

ls j ls
m j j, j 1,

,j

2 j1

2
2
2
1 2

L.S j, m j J L S j, m j j(j 1) l(l 1) s(s 1) j, m j

2
2

From one basis to the other = Clebsh Gordan

2 JUILLET 2014

MASTANI, Pune, INDIA, July 2014| PAGE 33

l 12 (2l+2)
j 1
2(2 l 1)
(2l)
l 2

1
s
2
l.s j, m j

2
2
2

j l s j, m j j(j 1) l(l 1) 12 ( 12 1) j, m j

2
2

l 1 (p orbitals)
p

(6)

l 2 (d orbitals)

(4) Ep3/2 2

(2)
(6)

d
2 JUILLET 2014

Ep1/2 p

Ed5/2 d

(10)

3
Ed3/2 d
(4)
2

MASTANI, Pune, INDIA, July 2014

| PAGE 34

Relativistic pseudo-potentials
Without SOC

But including other (scalar) relativistic effects

Vpseudo Vloc (r ) ElI lI Yl ,Iml

I

lI Yl ,Im

l , ml

VNL

Fe.pbe-nd-rrkjus.UPF

Pseudopotential type: ULTRASOFT

Method: Rappe Rabe Kaxiras Joannopoulos
Functional type: Perdew-Burke-Ernzerhof (PBE) exch-corr
Nonlinear core correction
scalar relativistic

With SOC

For technical details please contact Andrea dal Corso.

Vpseudo Vloc (r )

j l

VNLj

1
2

Vl Id Vl SO L.S Ylm Ylm

lm

Fe.rel-pbe-spn-rrkjus_psl.0.2.1.UPF
Pseudopotential type: ULTRASOFT
Method: Rappe Rabe Kaxiras Joannopoulos
Functional type: Perdew-Burke-Ernzerhof (PBE) exch-corr
Semi-core state in valence
Nonlinear core correction
2 JUILLET 2014 full relativistic
MASTANI, Pune, INDIA, July 2014| PAGE 35

SOME IMPORTANT TECHNICAL POINTS

Relativistic Pseudopotential (LDA pz /GGA pw91, pbe)

L.S

'

Is not diagonal in spins impossible to split up and down spins

= drastic increase of the computational cost

0
collinear

Non-collinear

Very dense K-points mesh

Check very carefully the influence of degauss

Use penalization when necessary (constrained_magnetization)

E ,
Very strict convergence threshold (conv_thr)

2 JUILLET 2014

MASTANI, Pune, INDIA, July 2014 | PAGE 36

A FEW THINGS ABOUT SOC

(r )

in TB (or LCAO) on site term I L.S I

Is short range (atomic-like)

(r ) Z4 Increases drastically with atomic number

ll ' Rlat (r )Rlat' (r ) (r) r 2 dr

0

0.05eV for 3d

0.5eV for 5d

The band structure depends on the magnetization axis

SOC is at the origin of the magnetocrystalline anisotropy

E ,

MCA 102 103 meV / atom in bulk Fe, Co, Ni

Much larger in nanostructures

MCA

meV / atom in bulk FePt L10

SOC is at the origin of the anisotropic magneto_resistance

2 JUILLET 2014

AMR 1% in bulk
larger in atomic wires

SOC is at the origin of the orbital moment

MASTANI, Pune, INDIA, July 2014 | PAGE 37

MAGNETOCRSYTALLINE ANISOTROPY
How to calculate MCA?
Brute force method (self-consistent)

n1
n2
EMCA Etot
Etot

where En1 and En2 are obtained from SCF calculation including SOC
In principle exact but very time consuming and hard to converge
One should use penalization techniques to obtain En for any direction
Force Theorem method

EMCA E

n1
band

n2
band

E1F

En ( E )dE
1

EF2

En 2 ( E )dE

n1
n2
Eband
and Eband
are band energies of NSCF calculations including SOC

Initial density is obtained from a SCF spin-collinear calculation and spin-moment

further rotated to appropriate spin direction
Very stable numerically but cannot be applied to systems with too large SOC.
2 JUILLET 2014

MASTANI, Pune, INDIA, July 2014 | PAGE 38

MCA: the local picture

Force Theorem in grand canonical ensemble

E1F

En1 ( E )dE

EF2

EF0

En 2 ( E )dE ( E EF0 )n( E )dE

EF0

Egc ( E EF0 )n( E )dE

Local decomposition

Projection onto atomic orbitals

Real space picture

EF0

E ( E EF0 )ni ( E )dE

gc
i

EF0

E (r ) ( E EF0 )n( E , r )dE

gc

The local decommposition in canonical picture leads to spurious oscillations

due to long range Friedel-like charge oscillations.. But the total MCA value is
kept due to charge conservation
2 JUILLET 2014

MASTANI, Pune, INDIA, July 2014 | PAGE 39

MCA: the local picture

MCA MCAi
i

MCA of a slab orginates from surface atoms of the outermost layers

fccCo

2 JUILLET 2014

Fe pyramid

MASTANI, Pune, INDIA, July 2014 | PAGE 40

PHYSICAL INSIGHT
Extended Heisenberg Hamiltonian

1
E J ij ei e j Fi (ei ) Dij .ei e j
2 i, j
i
ij
MCA

Fi (ei ) eit K i ei
F (ei ) K (n.ei ) 2

DM

Uniaxial anisotropy

Dzyaloshinskii-Moriya interaction

D only between first neighbours

(only exists in the absence of inversion symmetry)

DM favors non-collinear configurations
At the origin of skyrmion structures

DM=0

DM=0

DM0

MASTANI, Pune, INDIA, July 2014 | PAGE 41

SHAPE ANISOTROPY
m2

Classical dipole-dipole interaction

Edip (r )

0
3

m
.
m

m
.
r
m
.
r
1
2
1
2

4 r 3
r2

m1

Colllinear magnetism

Edip ( )

Breit interaction
(2 body relativistic term)

0
m1m2 1 3cos
4 r 3

For <54.74 FM

For >54.74 AF

In thin films: in-plane magnetization is always favored

2 JUILLET 2014

EMCA

Surface

Eshape

Volume

For ultra-thin films MCA is generally dominant

while the shape anisotropy always ends up by
dominating for thicker films

MASTANI, Pune, INDIA, July 2014 | PAGE 42

IMPORTANT THINGS I DID NOT TALK ABOUT

Orbital moment

m orb (r ) L
occ

m iorb (r ) L
occ

For modern theory of orbital magnetization see David Vanderbilt

DFT+U and orbital polarization

When using the rotationally invariant scheme of Liechtenstein (lda_plus_u_kind=1) the
Racah B parameter plays a crucial role in orbital magnetization

Spin-spirals and generalized Bloch theorem

Mapping DFT on model Hamiltonian Jii

Spin dynamics etc.
Spin-polarized transport
2 JUILLET 2014

MASTANI, Pune, INDIA, July 2014 | PAGE 43

ACKNOWLEDGEMENTS
TEAM

Alexander SMOGUNOV
Sylvain LATIL
Yannick DAPPE
Dongzhe LI (PhD)
COLLEAGUES

Chu Chu FU
Romain SOULAIROL (PhD)
Pascal THIBAUDEAU
David BEAUJOUAN (PhD)

2 JUILLET 2014

COLLEAGUES (Julich)

Stefan BLUGEL
Gustav BIHLMAYER
Timo SCHENA (Master)

MASTANI, Pune, INDIA, July 2014 | PAGE 44

BIBLIOGRAPHY
Electronic Structure
Basic Theory and Practical Methods
Richard Martin
Cambridge University Press

Theory of itinerant electron magnetism

Jrgen Kbler
Oxford Science Publications

Nouvelles mthodes pour le calcul ab-initio des proprits

statiques et dynamiques des matriaux magntiques.
Ralph Gebauer PhD thesis 1999
(in english)
2 JUILLET 2014

MASTANI, Pune, INDIA, July 2014 | PAGE 45

THANK YOU FOR YOUR ATTENTION

QUESTIONS?

COMMENTS?

| PAGE 46
MASTANI, Pune, INDIA, July 2014

2 JUILLET 2014