25th wien2k workshop boston college – 2018 › content › dam › bc1 › schools › mcas ›...

Relativistic effects &

magnetism

in WIEN2k

25th WIEN2k WorkshopBoston College – 2018

Xavier RocquefelteInstitut des Sciences Chimiques de Rennes

(UMR 6226) Université de Rennes 1, FRANCE

Talk constructed using the following documents: Slides of:

Robert Laskowski, Stefaan Cottenier, Peter Blaha and Georg Madsen

Books: - WIEN2k userguide, ISBN 3-9501031-1-2 - Electronic Structure: Basic Theory and Practical Methods, Richard M. Martin ISBN 0 521 78285 6 -  Relativistic Electronic Structure Theory. Part 1. Fundamentals, Peter Schewerdtfeger, ISBN 0 444 51249 7

Notes of: - Pavel Novak (Calculation of spin-orbit coupling)

http://www.wien2k.at/reg_user/textbooks/ - Robert Laskowski (Non-collinear magnetic version of WIEN2k package)

web: -  http://www2.slac.stanford.edu/vvc/theory/relativity.html -  wienlist digest - http://www.wien2k.at/reg_user/index.html -  wikipedia …

Few words about Special Theory of Relativity

Composed of photons (no mass) Speed of light = constant

c ≈ 137 au

Atomic units: ħ = me = e = 1

Light Matter

Composed of photons (no mass) Speed of light = constant

c ≈ 137 au

Speed of matter mass

v = f(mass)

mass = f(v)

Composed of atoms (mass)

Light Matter

Composed of photons (no mass)

Lorentz Factor (measure of the relativistic effects)

Speed of light = constant

c ≈ 137 au

Speed of matter mass

v = f(mass)

mass = f(v)

Momentum: p = γmv = Mv

Total energy:

Relativistic mass: M = γm (m: rest mass) 1

1 2 ≥

⎟ ⎠

⎞ ⎜ ⎝

Composed of atoms (mass)

E2 = p2c2 + m2c4 E = γmc2 = Mc2

( )22.1

⎟⎠

⎞⎜⎝

⎛−

γDetails for Au atom:

ccsve 58.013779)1( ==

Speed of the 1s electron (Bohr model):

+Ze e-

Lorentz factor (γ)

1 2 3 4 5 6 7 8 9

0 20 40 60 80 100 120

c ≈ 137 au

Speed (v)

Au(1s)

« Non-relativistic » particle: γ = 1

1s electron of Au atom = relativistic particle

Definition of a relativistic particle (Bohr model)

au 1 ) 1 ( : H = s v e

au 79 ) 1 ( : Au = s v e

00003 . 1 = γ

22 . 1 = γ n Z v e ∝

au 1 ) 1 ( : H = s v e

au 79 ) 1 ( : Au = s v e

00003 . 1 = γ

22 . 1 = γ n Z v e ∝

Me(1s-Au) = 1.22me

Relativistic effects

Relativistic increase in the mass of an electron with its velocity (when ve → c)

1) The mass-velocity correction

It has no classical relativistic analogue Due to small and irregular motions of an electron about its mean position (Zitterbewegung*)

2) The Darwin term

*Analysis of Erwin Schrödinger of the wave packet solutions of the Dirac equation for relativistic electrons in free space:The interference between positive and negative energy states produces what appears to be a fluctuation (at the speed of light) of the position of an electron around the median.

It has no classical relativistic analogue Due to small and irregular motions of an electron about its mean position (Zitterbewegung)

2) The Darwin term

It is the interaction of the spin magnetic moment (s) of an electron with the magnetic field induced by its own orbital motion (l)

3) The spin-orbit coupling

2) The Darwin term

The change of the electrostatic potential induced by relativity is an indirect effect of the core electrons on the valence electrons

4) Indirect relativistic effect

+Zeffe

One electron radial Schrödinger equation

Ψ=Ψ⎥⎦

⎤⎢⎣

⎡ +∇−=Ψ εVHS2

Ψ=Ψ⎥⎦

⎤⎢⎣

⎡+∇−=Ψ εV

HARTREE ATOMIC UNITS INTERNATIONAL UNITS

Atomic units: ħ = me = e = 1 1/(4 πε0) = 1

c = 1/ α ≈ 137 au

Ψ=Ψ⎥⎦

⎤⎢⎣

⎡ +∇−=Ψ εVHS2

Ψ=Ψ⎥⎦

⎤⎢⎣

⎡+∇−=Ψ εV

rZV −=

4πε−=

INTERNATIONAL UNITS

In a spherically symmetric potential

Atomic units: ħ = me = e = 1 1/(4 πε0) = 1

c = 1/ α ≈ 137 au

( ) ( )ϕθ ,,,,, mllnmln YrR=Ψ

( )( )

( ) ⎟⎟⎠

⎞⎜⎜⎝

∂+⎥⎦

⎤⎢⎣

⎡∂

∂+⎟⎠

⎞⎜⎝

⎛∂

∂=∇ 2

sin1sin

ϕθθθ

θθ rrrr

HARTREE ATOMIC UNITS

Ψ=Ψ⎥⎦

⎤⎢⎣

⎡ +∇−=Ψ εVHS2

( )lnln

rm ,,2

ε=⎥⎦

⎤⎢⎣

⎡ +++⎟⎟

⎞⎜⎜⎝

⎛−

In a spherically symmetric potential

Ψ=Ψ⎥⎦

⎤⎢⎣

⎡+∇−=Ψ εV

rZV −=

4πε−=

( )lnln

ln RRrllV

r ,,2,2

ε=⎥⎦

⎤⎢⎣

⎡ +++⎟⎟

⎞⎜⎜⎝

⎛−

INTERNATIONAL UNITS

( ) ( )ϕθ ,,,,, mllnmln YrR=Ψ

( )( )

( ) ⎟⎟⎠

⎞⎜⎜⎝

∂+⎥⎦

⎤⎢⎣

⎡∂

∂+⎟⎠

⎞⎜⎝

⎛∂

∂=∇ 2

sin1sin

ϕθθθ

θθ rrrr

HARTREE ATOMIC UNITS

Dirac Hamiltonian: a brief description

Dirac relativistic Hamiltonian provides a quantum mechanical description of electrons, consistent with the theory of special relativity.

Ψ=Ψ εDH with

E2 = p2c2 + m2c4

VcmpcH eD ++⋅= 2βα!!

Dirac relativistic Hamiltonian provides a quantum mechanical description of electrons, consistent with the theory of special relativity.

⎟⎟⎠

⎞⎜⎜⎝

σα ⎟⎟

⎞⎜⎜⎝

⎟⎟⎠

⎞⎜⎜⎝

1σ ⎟⎟⎠

⎞⎜⎜⎝

⎛ −=

σ ⎟⎟⎠

⎞⎜⎜⎝

(2×2) Pauli spin matrices

Momentum operator Rest mass

Electrostatic potential

VcmpcH eD ++⋅= 2βα!!

(2×2) unit and zero matrices

Ψ=Ψ εDH with

E2 = p2c2 + m2c4

Dirac Hamiltonian: a brief description

Dirac equation: HD and Ψ are 4-dimensional

Φ and χ are time-independent two-component spinors describing the spatial and spin-1/2 degrees of freedom

Ψ is a four-component single-particle wave function that describes spin-1/2 particles.

⎟⎟⎟⎟⎟

⎜⎜⎜⎜⎜

⎟⎟⎟⎟⎟

⎜⎜⎜⎜⎜

spin up

spin down

Large components (Φ)

Small components (χ)

In case of electrons:

⎟ ⎟ ⎠

⎞ ⎜ ⎜ ⎝

⎛ Φ =

Leads to a set of coupled equations for Φ and χ:

( ) ( )φεχσ 2cmVpc e−−=⋅!

( ) ( )χεφσ 2cmVpc e+−=⋅!

factor ∝ 1/(mec2)

For a free particle (i.e. V = 0):

( )( )

0ˆˆˆ0ˆˆˆˆˆˆ0ˆˆˆ0

⎟⎟⎟⎟⎟

⎜⎜⎜⎜⎜

⎟⎟⎟⎟⎟

⎜⎜⎜⎜⎜

+−−−

+−−

−−−−

cmppipcmpipp

ppipcmpippcm

⎟⎟⎟⎟⎟

⎜⎜⎜⎜⎜

⎛ ↑

cme⎟⎟⎟⎟⎟

⎜⎜⎜⎜⎜

⎛↓

Particles: up & down

⎟⎟⎟⎟⎟

⎜⎜⎜⎜⎜

− ↑

cme⎟⎟⎟⎟⎟

⎜⎜⎜⎜⎜

Antiparticles: up & down

Solution in the slow particle limit (p=0)

Non-relativistic limit decouples Ψ1 from Ψ2

and Ψ3 from Ψ4

For a free particle (i.e. V = 0):

( )( )

0ˆˆˆ0ˆˆˆˆˆˆ0ˆˆˆ0

⎟⎟⎟⎟⎟

⎜⎜⎜⎜⎜

⎟⎟⎟⎟⎟

⎜⎜⎜⎜⎜

+−−−

+−−

−−−−

cmppipcmpipp

ppipcmpippcm

⎟⎟⎟⎟⎟

⎜⎜⎜⎜⎜

⎛ ↑

cme⎟⎟⎟⎟⎟

⎜⎜⎜⎜⎜

⎛↓

Particles: up & down

⎟⎟⎟⎟⎟

⎜⎜⎜⎜⎜

− ↑

cme⎟⎟⎟⎟⎟

⎜⎜⎜⎜⎜

Antiparticles: up & down

Solution in the slow particle limit (p=0)

Non-relativistic limit decouples Ψ1 from Ψ2

and Ψ3 from Ψ4

For a spherical potential V(r):

( ) ⎟ ⎟ ⎠

⎞ ⎜ ⎜ ⎝

⎛ Υ -

Υ = ⎟ ⎟

⎞ ⎜ ⎜ ⎝

⎛ Φ = Ψ

κσ nκ

κσ nκ χ r f i

gnκ and fnκ are Radial functions

Yκσ are angular-spin functions

2slj +=

( )21+−= jsκ

1,1−+=s

Dirac equation in a spherical potential

The resulting equations for the radial functions (gnκ and fnκ) are simplified if we define:

2' cme−= εε ( ) ( )22

'crVmrM ee

−+=ε

Energy: Radially varying mass:

2' cme−= εε ( ) ( )22

'crVmrM ee

−+=ε

Then the coupled equations can be written in the form of the radial eq.:

Darwin term

Spin-orbit coupling

( ) ( )11 +=+ llκκNote that:

Mass-velocity effect

( ) ( )κκ

κ εκ

dVcMdr

dgdrdV

−−⎥⎦

⎤⎢⎣

⎡ +++⎟

⎞⎜⎝

⎛−!!!!

( )lnln

rm ,,2

ε=⎥⎦

⎤⎢⎣

⎡ +++⎟⎟

⎞⎜⎜⎝

⎛−

!! One electron radial Schrödinger equation in a spherical potential

2' cme−= εε ( ) ( )22

'crVmrM ee

−+=ε

( ) ( )κκ

κ εκ

dVcMdr

dgdrdV

−−⎥⎦

⎤⎢⎣

⎡ +++⎟

⎞⎜⎝

⎛−!!!!

( ) ( )κκ

κε nn

df 1'1 −+−=

Then the coupled equations can be written in the form of the radial eq.:

and Darwin term

Spin-orbit coupling

( ) ( )11 +=+ llκκNote that:

Due to spin-orbit coupling, Ψ is not an eigenfunction of spin (s) and angular orbital moment (l). Instead the good quantum numbers are j and κ

No approximation has been made so

Scalar relativistic approximation

Approximation that the spin-orbit term is small ⇒ neglect SOC in radial functions (and treat it by perturbation theory)

nln gg ~→κ nln ff ~→κ

~12 22

ε=−⎥⎦

⎤⎢⎣

⎡ +++⎟

⎞⎜⎝

⎛−!!!

cMf nl

2~ !=and with the normalization condition: ( ) 1 ~~ 222 =+∫ drrfg nlnl

No SOC ⇒ Approximate radial functions:

Scalar relativistic approximation

Approximation that the spin-orbit term is small ⇒ neglect SOC in radial functions (and treat it by perturbation theory)

nln gg ~→κ nln ff ~→κ

~12 22

ε=−⎥⎦

⎤⎢⎣

⎡ +++⎟

⎞⎜⎝

⎛−!!!

cMf nl

2~ !=and with the normalization condition: ( ) 1 ~~ 222 =+∫ drrfg nlnl

No SOC ⇒ Approximate radial functions:

The four-component wave function is now written as:

Inclusion of the spin-orbit coupling in “second variation” (on the large component only) ( )

( ) ⎟ ⎟ ⎠

⎞ ⎜ ⎜ ⎝

⎛ Υ -

Υ = ⎟ ⎟

⎞ ⎜ ⎜ ⎝

⎛ Φ = Ψ

lm nl χ r f i

∼ ∼

ψψεψ ~~~SOHH +=

⎟⎟⎠

⎞⎜⎜⎝

2 ldrdVrcM

!!" σ

Φ ∼

is a pure spin state

χ ∼ is a mixture of up and down spin states

Relativistic effects in a solid

For a molecule or a solid:

Relativistic effects originate deep inside the core.

It is then sufficient to solve the relativistic equations in a spherical atomic geometry (inside the atomic spheres of WIEN2k).

Justify an implementation of the relativistic effects only inside the muffin-tin atomic spheres

SOC: Spin orbit coupling

Implementation in WIEN2k

Atomic sphere (RMT) Region

Core electrons

Valence electrons

« Fully » relativistic

Spin-compensated Dirac equation

Scalar relativistic (no SOC)

Possibility to add SOC (2nd variational)

Implementation in WIEN2k

Interstitial Region

Valence electrons

Not relativistic

SOC: Spin orbit coupling

Atomic sphere (RMT) Region

Core electrons

Valence electrons

« Fully » relativistic

Spin-compensated Dirac equation

Scalar relativistic (no SOC)

Possibility to add SOC (2nd variational)

Atomic sphere (RMT) RegionAtomic sphere (RMT) Region

CoreelectronsCore

electrons

« Fully »relativistic

Spin-compensatedDirac equation

CoreelectronsCore

electrons

17 0.00 0 1,-1,2 ( n,κ,occup) 2,-1,2 ( n,κ,occup) 2, 1,2 ( n,κ,occup) 2,-2,4 ( n,κ,occup) 3,-1,2 ( n,κ,occup) 3, 1,2 ( n,κ,occup) 3,-2,4 ( n,κ,occup) 3, 2,4 ( n,κ,occup) 3,-3,6 ( n,κ,occup) 4,-1,2 ( n,κ,occup) 4, 1,2 ( n,κ,occup) 4,-2,4 ( n,κ,occup) 4, 2,4 ( n,κ,occup) 4,-3,6 ( n,κ,occup) 5,-1,2 ( n,κ,occup) 4, 3,6 ( n,κ,occup) 4,-4,8 ( n,κ,occup) 0

case.inc for Au atom

s 0 1/2 -1 2

p 1 3/2 1/2 1 -2 2 4

d 2 5/2 3/2 2 -3 4 6

f 3 7/2 5/2 3 -4 6 8

l s=+1

j=l+s/2 κ=-s(j+1/2) occupation

s=-1 s=+1 s=-1 s=+1 s=-1

For spin-polarized potential, spin up and spin down are calculated separately, the density is averaged according to the occupation number

specified in case.inc file.

Core states: fully occupied → spin-compensated Dirac

equation (include SOC)

Implementation in WIEN2k: core electrons

1s1/2 → 2s1/2

2p1/2 → 2p3/2 → 3s1/2 3p1/2 3p3/2 3d3/2 → 3d5/2 → 4s1/2 4p1/2 4p3/2 4d3/2 4d5/2 5s1/2 4f5/2 → 4f7/2 →

CoreelectronsCore

electrons

CoreelectronsCore

electrons

17 0.00 0 1,-1,2 ( n,κ,occup) 2,-1,2 ( n,κ,occup) 2, 1,2 ( n,κ,occup) 2,-2,4 ( n,κ,occup) 3,-1,2 ( n,κ,occup) 3, 1,2 ( n,κ,occup) 3,-2,4 ( n,κ,occup) 3, 2,4 ( n,κ,occup) 3,-3,6 ( n,κ,occup) 4,-1,2 ( n,κ,occup) 4, 1,2 ( n,κ,occup) 4,-2,4 ( n,κ,occup) 4, 2,4 ( n,κ,occup) 4,-3,6 ( n,κ,occup) 5,-1,2 ( n,κ,occup) 4, 3,6 ( n,κ,occup) 4,-4,8 ( n,κ,occup) 0

case.inc for Au atom

s 0 1/2 -1 2

p 1 3/2 1/2 1 -2 2 4

d 2 5/2 3/2 2 -3 4 6

f 3 7/2 5/2 3 -4 6 8

l s=+1

j=l+s/2 κ=-s(j+1/2) occupation

s=-1 s=+1 s=-1 s=+1 s=-1

For spin-polarized potential, spin up and spin down are calculated separately, the density is averaged according to the occupation number

specified in case.inc file.

Core states: fully occupied → spin-compensated Dirac

equation (include SOC)

Implementation in WIEN2k: core electrons

Valence electrons INSIDE atomic spheres are treated within scalar relativistic approximation [1] if RELA

is specified in case.struct file (by default).

[1] Koelling and Harmon, J. Phys. C (1977)

Title F LATTICE,NONEQUIV.ATOMS: 1 225 Fm-3m MODE OF CALC=RELA unit=bohr 7.670000 7.670000 7.670000 90.000000 90.000000 90.000000 ATOM 1: X=0.00000000 Y=0.00000000 Z=0.00000000 MULT= 1 ISPLIT= 2 Au1 NPT= 781 R0=0.00000500 RMT= 2.6000 Z: 79.0 LOCAL ROT MATRIX: 1.0000000 0.0000000 0.0000000 0.0000000 1.0000000 0.0000000 0.0000000 0.0000000 1.0000000 48 NUMBER OF SYMMETRY OPERATIONS

♦ no κ dependency of the wave function, (n,l,s) are still good quantum numbers ♦ all relativistic effects are included except SOC ♦ small component enters normalization and calculation of charge inside spheres ♦ augmentation with large component only ♦ SOC can be included in « second variation »

Valence electrons in interstitial region are treated classically

Valence electronsValence electrons

Scalar relativistic(no SOC)

Possibility to add SOC(2nd variational)

Implementation in WIEN2k: valence electrons

SOC is added in a second variation (lapwso):

- First diagonalization (lapw1): - Second diagonalization (lapwso):

1111 Ψ=Ψ εH( ) Ψ=Ψ+ εSOHH1

The second equation is expanded in the basis of first eigenvectors (Ψ1)

( ) ΨΨ=ΨΨΨΨ+∑ jiN

jjij H 11111 εεδ

sum include both up/down spin states → N is much smaller than the basis size in lapw1

SOC is added in a second variation (lapwso):

- First diagonalization (lapw1): - Second diagonalization (lapwso):

1111 Ψ=Ψ εH( ) Ψ=Ψ+ εSOHH1

The second equation is expanded in the basis of first eigenvectors (Ψ1)

( ) ΨΨ=ΨΨΨΨ+∑ jiN

jjij H 11111 εεδ

sum include both up/down spin states → N is much smaller than the basis size in lapw1

♦ SOC is active only inside atomic spheres, only spherical potential (VMT) is taken into account, in the polarized case spin up and down parts are averaged.

♦ Eigenstates are not pure spin states, SOC mixes up and down spin states

♦ Off-diagonal term of the spin-density matrix is ignored. It means that in each SCF cycle the magnetization is projected on the chosen direction (from case.inso)

VMT: Muffin-tin potential (spherically symmetric)

Controlling spin-orbit coupling in WIEN2k

♦ Do a regular scalar-relativistic “scf” calculation

♦ save_lapw

♦ initso_lapw

WFFIL 4 1 0 llmax,ipr,kpot -10.0000 1.50000 emin,emax (output energy window) 0. 0. 1. direction of magnetization (lattice vectors) NX number of atoms for which RLO is added NX1 -4.97 0.0005 atom number,e-lo,de (case.in1), repeat NX times 0 0 0 0 0 number of atoms for which SO is switch off; atoms

• case.inso:

• case.in1(c): (…) 2 0.30 0.005 CONT 1 0 0.30 0.000 CONT 1 K-VECTORS FROM UNIT:4 -9.0 4.5 65 emin/emax/nband

• symmetso (for spin-polarized calculations only)

♦ run(sp)_lapw -so -so switch specifies that scf cycles will include SOC

The w2web interface is helping you

Non-spin polarized case

The w2web interface is helping you

Spin polarized case

Relativistic effects in the solid: Illustration

LDA overbinding (7%)

No difference NREL/SREL

Bulk modulus: -  NREL: 131.4 GPa -  SREL: 131.5 GPa -  Exp.: 130 GPa

hcp-Be Z = 4

175 180 185 190 195 200 205 210

No difference NREL/SREL

Bulk modulus: -  NREL: 131.4 GPa -  SREL: 131.5 GPa -  Exp.: 130 GPa

Clear difference NREL/SREL

Bulk modulus: -  NREL: 344 GPa -  SREL: 447 GPa -  Exp.: 462 GPa

hcp-Be Z = 4

hcp-Os Z = 76

175 180 185 190 195 200 205 210 ♦ Scalar-relativistic (SREL):

-  LDA overbinding (2%) -  Bulk modulus: 447 GPa

+ spin-orbit coupling (SREL+SO): -  LDA overbinding (1%) -  Bulk modulus: 436 GPa

⇒ Exp. Bulk modulus: 462 GPa

hcp-Be Z = 4

hcp-Os Z = 76

exp SREL+SO

2) The Darwin term

The change of the electrostatic potential induced by relativity is an indirect effect of the core electrons on the valence electrons

4) Indirect relativistic effect

+Zeffe

Zansr 02

)1( = bohr 10 ==αcm

bohr 013.0791)1( ==sr

r 2 ρ (e/ bohr )

0.00 r ( bohr )

0.01 0.02 0.03 0.04 0.05 0.06 0

50 Non relativistic (l=0)

r 2 ρ (e/ bohr )

0.00 r ( bohr )

0.01 0.02 0.03 0.04 0.05 0.06 0

50 Non relativistic (l=0)

r 2 ρ (e/ bohr )

0.00 r ( bohr )

0.01 0.02 0.03 0.04 0.05 0.06 0

50 Radius of the 1s orbit (Bohr model):

+Ze e-

c = 1/ α ≈ 137 au

(1) Relativistic orbital contraction

[ ]γα0

cMRELAa

ee mmM 22.1=⋅= γ

Zansr 02

)1( = bohr 10 ==αmc

bohr 013.0791)1( ==sr

r 2 ρ (e/ bohr )

0.00 r ( bohr )

0.01 0.02 0.03 0.04 0.05 0.06 0

50 Non relativistic (l=0) Relativistic ( κ = - 1)

r 2 ρ (e/ bohr )

0.00 r ( bohr )

0.01 0.02 0.03 0.04 0.05 0.06 0

50 Non relativistic (l=0) Relativistic ( κ = - 1)

r 2 ρ (e/ bohr )

0.00 r ( bohr )

0.01 0.02 0.03 0.04 0.05 0.06 0

50 Non relativistic (l=0) Relativistic ( κ = - 1) Relativistic ( κ = - 1)

20% Orbital contraction

Radius of the 1s orbit (Bohr model):

+Ze e-

In Au atom, the relativistic mass (M) of the 1s electron is 22% larger than

the rest mass (m)

bohr 010 . 0 22 . 1 1

79 1 ) 1 ( 0

2 = = =

Z n s r

0 2 4 6 0.0

0.5 r 2 ρ (e/ bohr )

r ( bohr )

Non relativistic (l=0) Relativistic ( κ = - 1)

0 2 4 6 0.0

0.5 r 2 ρ (e/ bohr )

r ( bohr )

Non relativistic (l=0) Relativistic ( κ = - 1) Relativistic ( κ = - 1)

Orbital contraction

ns orbitals (with n > 1) contract due to orthogonality to 1s

( )0046.1

096.01

⎟⎠

⎞⎜⎝

⎛−

cnZsve 096.017.13

679)6( ====

Direct relativistic effect (mass enhancement) → contraction of 0.46% only

However, the relativistic contraction of the 6s orbital is large (>20%)

Relativistic correction (%)

1s 2s 4s 3s 5s 6s

( )NRELA

NRELARELA

EEE −

r 2 ρ (e/ bohr )

0.00 r ( bohr )

0.01 0.02 0.03 0.04 0.05 0.06 0

Orbital contraction

Au 1s 0 2 4 6 0.0

0.5 r 2 ρ (e/ bohr )

r ( bohr )

r 2 ρ (e/ bohr )

Orbital contraction

(1) Orbital Contraction: Effect on the energy

(2) Spin-Orbit splitting of p states

r 2 ρ (e/ bohr )

r ( bohr ) 0.0 0.5 1.5 2.0

r 2 ρ (e/ bohr )

r ( bohr ) 2.5

Non relativistic (l=1) Non relativistic (l=1)

j=3/2 (κ=-2)

orbital moment

j=1+1/2=3/2

♦ Spin-orbit splitting of l-quantum number

r 2 ρ (e/ bohr ) r 2 ρ (e/ bohr ) Non relativistic (l=1) Relativistic ( κ = - 2) Non relativistic (l=1) Relativistic ( κ = - 2)

♦ p3/2 (κ=-2): nearly same behavior than non-relativistic p-state

1.0 r ( bohr )

0.0 0.5 1.5 2.0 r ( bohr )

2.5 0.0

j=1/2 (κ=1) j=1-1/2=1/2

orbital moment

j=1-1/2=1/2

r 2 ρ (e/ bohr ) r 2 ρ (e/ bohr ) Non relativistic (l=1)

Relativistic ( κ =1)

Non relativistic (l=1)

Relativistic ( κ =1)

♦ p1/2 (κ=1): markedly different behavior than non-relativistic p-state

gκ=1 is non-zero at nucleus

1.0 r ( bohr )

0.0 0.5 1.5 2.0 r ( bohr )

2.5 0.0

j=1/2 (κ=1)

(κ=-2)

j=1-1/2=1/2

orbital moment

j=1+1/2=3/2 j=1-1/2=1/2

Ej=3/2 ≠ Ej=1/2

r 2 ρ (e/ bohr ) r 2 ρ (e/ bohr ) Non relativistic (l=1) Relativistic ( κ = - 2) Relativistic ( κ =1)

Non relativistic (l=1) Relativistic ( κ = - 2) Relativistic ( κ =1)

♦ p1/2 (κ=1): markedly different behavior than non-relativistic p-state

gκ=1 is non-zero at nucleus

1.0 r ( bohr )

0.0 0.5 1.5 2.0 r ( bohr )

2.5 0.0

2p1/2 2p3/2

3p1/2 3p3/2 4p1/2 4p3/2 5p1/2 5p3/2

( )NRELA

NRELARELA

EEE −

κ=1 κ=-2

Scalar-relativistic p-orbital is similar to p3/2 wave function, but Ψ does not contain p1/2 radial basis function

r2ρ (e/bohr)r2ρ (e/bohr)Non relativistic (l=1)Relativistic (κ=-2)Relativistic (κ=1)

Non relativistic (l=1)Relativistic (κ=-2)Relativistic (κ=1)

1.0r (bohr)

0.0 0.5 1.5 2.0r (bohr)

2.50.0

(3) Orbital expansion: Au(d) states

Higher l-quantum number states expand due to better shielding of nucleus charge from contracted s-states

+Ze -e

Non-relativistic (NREL)

+Ze -e

Non-relativistic (NREL)

+Zeff1e

Zeff1 = Z- σ(NREL)

+Ze -e

+Zeff1e +Zeff2e

Zeff2 = Z- σ(REL)

Non-relativistic (NREL) Relativistic (REL)

Zeff1 = Z- σ(NREL) Zeff1 > Zeff2

+Ze -e

+Zeff1e +Zeff2e

Zeff2 = Z- σ(REL)

Non-relativistic (NREL) Relativistic (REL)

Indirect relativistic effect

Zeff1 > Zeff2 Zeff1 = Z- σ(NREL)

3d3/2 3d5/2 4d3/2 4d5/2

5d3/2 5d5/2

4f5/2 4f7/2 ( )

NRELARELA

EEE −

0 1 2 3 0.0

0.4 r 2 ρ (e/ bohr )

r ( bohr )

Non relativistic (l=2) Relativistic ( κ =2) Relativistic ( κ = - 3)

4 0 1 2 3 0.0

0.4 r 2 ρ (e/ bohr )

r ( bohr )

4 0.0 0.1 0.2 0.3 0

4 r 2 ρ (e/ bohr )

r ( bohr )

0.4 0.0 0.1 0.2 0.3 0

4 r 2 ρ (e/ bohr )

r ( bohr )

κ=2 κ=-3

κ=3 κ=-4

Orbital expansion

Au 3d Au 5d

1s 2s 4s 2p1/2 2p3/2

3d3/2 3d5/2

3s 3p1/2 3p3/2

5s 6s 4p1/2 4p3/2 5p1/2 5p3/2

4d3/2 4d5/2

5d3/2 5d5/2

4f5/2 4f7/2

( )NRELA

NRELARELA

EEE −

Relativistic effects on the Au energy levels

Atomic spectra of gold

Orbital contraction

SO splitting

SO splitting Orbital expansion

Ag – Au: the differences (DOS & optical prop.)

Relativistic semicore states: p1/2 orbitals

Electronic structure of fcc Th, SOC with 6p1/2 local orbital

J.Kuneš, P.Novak, R.Schmid, P.Blaha, K.Schwarz, Phys.Rev.B. 64, 153102 (2001)

Energy vs. basis size DOS with and without p1/2

p1/2 included

p1/2 not included

SOC in magnetic systems

SOC couples magnetic moment to the lattice

Symmetry operations acts in real and spin space

♦direction of the exchange field matters (input in case.inso)

♦number of symmetry operations may be reduced (reflections act differently on spins than on positions)

♦time inversion is not symmetry operation (do not add an inversion for klist)

♦initso_lapw (must be executed) detects new symmetry setting

[100] [010] [001] [110]

A A A A

A B B -

B A B - B B A B

Direction of magnetization

Relativity in WIEN2k: Summary

WIEN2k offers several levels of treating relativity: ♦non-relativistic: select NREL in case.struct (not recommended)

♦standard: fully-relativistic core, scalar-relativistic valence

mass-velocity and Darwin s-shift, no spin-orbit interaction

♦”fully”-relativistic:

adding SO in “second variation” (using previous eigenstates as basis)

adding p1/2 LOs to increase accuracy (caution!!!)

x lapw1 (increase E-max for more eigenvalues, to have x lapwso basis for lapwso)

x lapw2 –so -c SO ALWAYS needs complex lapw2 version

♦Non-magnetic systems:

SO does NOT reduce symmetry. initso_lapw just generates case.inso and case.in2c.

♦Magnetic systems:

symmetso detects proper symmetry and rewrites case.struct/in*/clm*

Magnetic coupling &

Magnetic anisotropy

INTRODUCTION

Magnetic properties:

ü  Spin-state (high/low) ü  Long-range/short-range orders ü  Collinear / non-collinear ü  Magnetic anisotropy ü  Magnetic frustration ü  Magnetic exchange

Energy scale (eV) 100 10-3 10-6

Spin-State Magnetic exchange Long-range order

Magnetic anisotropy

INTRODUCTION

Paramagnetic(PM)

Ferrimagneticorder

Ferromagnetic(FM) order

Antiferromagnetic(AFM) order

COLLINEAR MAGNETISM

0 50 100 150 200 250 300

χmol(emu/mol)

PM without long range interaction

Magnetic susceptibility of a ferromagnetic (FM) compound

COLLINEAR MAGNETISM

0 50 100 150 200 250 300

χmol(emu/mol)

COLLINEAR MAGNETISM

0 50 100 150 200 250 300

χmol(emu/mol)

COLLINEAR MAGNETISM

0 50 100 150 200 250 300

χmol(emu/mol)

COLLINEAR MAGNETISM

0 50 100 150 200 250 300

χmol(emu/mol)

COLLINEAR MAGNETISM

Magnetic susceptibility of an antiferromagnetic (AFM) compound

0 50 100 150 200 250 300

χmol(emu/mol)

PM without long-range interactions

COLLINEAR MAGNETISM

0 50 100 150 200 250 300

χmol(emu/mol)

COLLINEAR MAGNETISM

0 50 100 150 200 250 300

χmol(emu/mol)

0,01 JAF

COLLINEAR MAGNETISM

0 50 100 150 200 250 300

χmol(emu/mol)

0 50 100 150 200 250 300

χmol(emu/mol)0,02

AF0,01

TC TNCurie temperature Néel temperature

Ferromg order↑ when kT ↓

Antiferromagnetic Ferromagnetic

JF JAF

Ferromagnetic exchange: JF < 0 Antiferromagnetic exchange: JAF > 0

NON-COLLINEAR MAGNETISM

AFM with 2 subnetworks having different

magnetization directions

⇒ weak ferromagnetism

Frustrated AFM

Topologic frustration FM-AFM competition

?J1 J1

?J1 : FM J2 : AFM

NON-COLLINEAR MAGNETISM

AFM with 2 subnetworks having different

magnetization directions

⇒ weak ferromagnetism

Frustrated AFM

Topologic frustration FM-AFM competition

?J1 J1

?J1 : FM J2 : AFM

Estimation of magnetic coupling parameters

Estimation of J can be done by mapping energy differences onto the general Heisenberg Spin Hamiltonian:

H = H0 + Jij!Si.

i< j∑

Jij: spin exchange parameter between the

spin sites i and j

Jij > 0 ⇒ AFM Jij < 0 ⇒ FM

Long-range order

H = H0 + Jij!Si.

i< j∑

spin sites i and j

Long-range order

Eα = α H α = E0 +S2 Jiji< j∑ σ iσ j

S: Spin hold by the magnetic center

σi = ±1 (up or down spin)

H = H0 + Jij!Si.

i< j∑

spin sites i and j

Long-range order

S: Spin hold by the magnetic center

σi = ±1 (up or down spin)

Example of a spin-half dimer (S = ½) To estimate the J12 value, 2 total energy calculations are needed:

EFM = E0 +14J12 EAFM = E0 +−

J12 = 2 EFM −EAFM( )σ1 = +1 σ2 = +1 σ1 = +1 σ2 = -1

Illustration with NiO: NaCl structure, A-type AFM along [111]

Ni2+ -> S = 1

2 inequivalent Ni sites in the rhombohedral unit cell (S.G. R-3m)

J: magnetic coupling defined by Ni1-O-Ni2 path (angle : 180°)

12J / unit cell

2J / f.u.

Ni2+ -> S = 1

2 inequivalent Ni sites in the rhombohedral unit cell (S.G. R-3m)

J: magnetic coupling defined by Ni1-O-Ni2 path (angle : 180°)

12J / unit cell

2J / f.u.

J = (EFM −EAFM ) / 4EFM = E0 + 2J EAFM = E0 − 2J

Magnetic structure of NiO – GGA+U calculations

PRB 62, 16392 (2000)

Ni M.M. (exp.) = 1.64 – 1.9 μB

PRB 62, 16392 (2000)

Eg (exp.) = 3 – 4.4 eV

AFM (more stable) Exp. Ground State: AFM

J (exp.) = 19 meV

PRB 6, 3447 (1972)

Estimation of the magnetic anisotropy

♦ Do a regular scalar-relativistic “scf” calculation

♦ save_lapw

♦ initso_lapw

WFFIL 4 1 0 llmax,ipr,kpot -10.0000 1.50000 emin,emax (output energy window) 0. 0. 1. direction of magnetization (lattice vectors) NX number of atoms for which RLO is added NX1 -4.97 0.0005 atom number,e-lo,de (case.in1), repeat NX times 0 0 0 0 0 number of atoms for which SO is switch off; atoms

• case.inso:

• case.in1(c): (…) 2 0.30 0.005 CONT 1 0 0.30 0.000 CONT 1 K-VECTORS FROM UNIT:4 -9.0 4.5 65 emin/emax/nband

• symmetso (for spin-polarized calculations only)

♦ run(sp)_lapw -so -so switch specifies that scf cycles will include SOC

Estimation of the Magneto-crystalline Anisotropy Energy (MAE) of CuO

Allows to define the magnetization

easy and hard axes

Here we have considered the following expression:

MAE = E[u v w] – E[easy axis]

[1] X. Rocquefelte, P. Blaha, K. Schwarz, S. Kumar, J. van den Brink, Nature Comm. 4, 2511 (2013)

MAE (μeV)

Magnetization axis

Hard axis

Easy axis

Hard axis

E[uvw] is the energy deduced from spin-orbit calculations with the magnetization along the [uvw]

crystallographic direction

Estimation of the Magneto-crystalline Anisotropy Energy (MAE) of CuO

E[uvw] is the energy deduced from spin-orbit calculations with the magnetization along the [uvw]

crystallographic direction

[-101]

[10-1]

[0-10][-10-1][010]

[1] X. Rocquefelte, P. Blaha, K. Schwarz, S. Kumar, J. van den Brink, Nature Comm. 4, 2511 (2013)

Allows to define the magnetization

easy and hard axes

Here we have considered the following expression:

MAE = E[u v w] – E[easy axis]

Relativistic effects &

Non-collinear magnetism

(WIEN2k / WIENncm)

Pauli Hamiltonian for magnetic systems

( ) ...2

+⋅+⋅++∇−= lBVm

H effBeffe

!!!!"σζσµ

2x2 matrix in spin space, due to Pauli spin operators

⎟⎟⎠

⎞⎜⎜⎝

1σ ⎟⎟⎠

⎞⎜⎜⎝

⎛ −=

σ ⎟⎟⎠

⎞⎜⎜⎝

( ) ...2

+⋅+⋅++∇−= lBVm

H effBeffe

!!!!"σζσµ

Wave function is a 2-component vector (spinor) – It corresponds to the large components of the dirac wave function (small components are neglected)

⎟⎟⎠

⎞⎜⎜⎝

Ψ=⎟⎟

⎞⎜⎜⎝

1 εPHspin up spin down

⎟⎟⎠

⎞⎜⎜⎝

1σ ⎟⎟⎠

⎞⎜⎜⎝

⎛ −=

σ ⎟⎟⎠

⎞⎜⎜⎝

( ) ...2

+⋅+⋅++∇−= lBVm

H effBeffe

!!!!"σζσµ

Effective electrostatic potential

Effective magnetic field

xcHexteff VVVV ++= xcexteff BBB +=

Exchange-correlation potential

Exchange-correlation field

( ) ...2

+⋅+⋅++∇−= lBVm

H effBeffe

!!!!"σζσµ

Effective electrostatic potential

Effective magnetic field

Spin-orbit coupling

drdVrcMe

=ζxcHexteff VVVV ++= xcexteff BBB +=

Exchange-correlation potential

Exchange-correlation field

Many-body effects which are defined within DFT LDA or GGA

Exchange and correlation

From DFT exchange correlation energy:

( )( ) ( ) ( )[ ] 3 , , drmrrmrE homxcxc

!!ρερρ ∫=

Local function of the electronic density (ρ) and the magnetic moment (m)

Definition of Vxc and Bxc (functional derivatives):

( )ρρ

mEV xcxc

!, ( )mmEB xc

LDA expression for Vxc and Bxc:

( ) ( )ρρε

ρρε∂

mmVhomxchom

!! ,, ( )m

xc ˆ,∂

!! ρε

Bxc is parallel to the magnetization density vector (m) ^

Direction of magnetization vary in space, thus spin-orbit term is present

( ) ...2

+⋅+⋅++∇−= lBVm

H effBeffe

!!!!"σζσµ

( )εψψ

⎟⎟⎟⎟

⎜⎜⎜⎜

+−+∇−+

−+++∇−

zBeffe

yxBzBeffe

iBBBVm

♦ Non-collinear magnetic moments ⎟⎟⎠

⎞⎜⎜⎝

ψψ Ψ1 and Ψ2 are

non-zero

♦ Solutions are non-pure spinors

Collinear magnetism

Magnetization in z-direction / spin-orbit is not present

( ) ...2

+⋅+⋅++∇−= lBVm

H effBeffe

!!!!"σζσµ

εψψµ

⎟⎟⎟⎟

⎜⎜⎜⎜

+−+∇−

+++∇−

zBeffe

♦ Collinear magnetic moments

♦ Solutions are pure spinors ⎟⎟⎠

⎞⎜⎜⎝

⎛=↑ 0

1ψψ ⎟⎟⎠

⎞⎜⎜⎝

⎛=↓

↓↑ ≠ εε ♦ Non-degenerate energies

Non-magnetic calculation

No magnetization present, Bx = By = Bz = 0 and no spin-orbit coupling

( ) ...2

+⋅+⋅++∇−= lBVm

H effBeffe

!!!!"σζσµ

εψψ =

⎟⎟⎟⎟

⎜⎜⎜⎜

+∇−

⎟⎟⎠

⎞⎜⎜⎝

⎛=↑ 0ψ

ψ ⎟⎟⎠

⎞⎜⎜⎝

⎛=↓ ψ

↓↑ = εε

♦ Solutions are pure spinors

♦ Degenerate spin solutions

Magnetism and WIEN2k

Wien2k can only handle collinear or non-magnetic cases

run_lapw script:

x lapw0 x lapw1 x lapw2 x lcore x mixer

non-magnetic case

m = n↑ – n↓ = 0

run_lapw script:

x lapw0 x lapw1 –up x lapw1 -dn x lapw2 –up x lapw2 -dn x lcore –up x lcore -dn x mixer

magnetic case

m = n↑ – n↓ ≠ 0 DOS

Magnetism and WIEN2k

Spin-polarized calculations

♦ runsp_lapw script (unconstrained magnetic calc.)

♦ runfsm_lapw -m value (constrained moment calc.)

♦ runafm_lapw (constrained anti-ferromagnetic calculation)

♦ spin-orbit coupling can be included in second variational step

♦ never mix polarized and non-polarized calculations in one case directory !!!

♦ code based on Wien2k (available for Wien2k users)

In case of non-collinear spin arrangements WIENncm (WIEN2k clone) has to be used:

♦ structure and usage philosophy similar to Wien2k ♦ independent source tree, independent installation

WIENncm properties:

♦ real and spin symmetry (simplifies SCF, less k-points)

♦ constrained or unconstrained calculations (optimizes magnetic moments)

♦ SOC in first variational step, LDA+U

♦ Spin spirals

For non-collinear magnetic systems, both spin channels have to be considered simultaneously

runncm_lapw script:

xncm lapw0 xncm lapw1 xncm lapw2 xncm lcore xncm mixer

Relation between spin density matrix and magnetization

mz = n↑↑ – n↓↓ ≠ 0

mx = ½(n↑↓ + n↓↑) ≠ 0

my = i½(n↑↓ - n↓↑) ≠ 0

WienNCM: Spin spirals

Transverse spin wave

qR !!⋅=α

R ( ) ( )( )θθ cos , sinsin , cos nnn RqRqmm

!!!!!⋅⋅=

♦ spin-spiral is defined by a vector q given in reciprocal space and an angle θ between magnetic moment and rotation axis.

♦ Rotation axis is arbitrary (no SOC) – fixed as z-axis in WIENNCM

⇒ Translational symmetry is lost !

⇒ But WIENncm is using the generalized Bloch theorem. The calculation of spin waves only requires one unit cell for even incommensurate modulation q vector.

WienNCM: Usage

1. Generate the atomic and magnetic structures

2. Run initncm (initialization script)

3. Run the NCM calculation:

♦ Create atomic structure

♦ Create magnetic structure

See utility programs: ncmsymmetry, polarangles, …

♦ xncm (WIENncm version of x script)

♦ runncm (WIENncm version of run script)

More information on the manual (Robert Laskowski)

rolask@theochem.tuwien.ac.at

25th wien2k workshop boston college – 2018 › content › dam › bc1 › schools › mcas ›...

Documents

methods available in wien2k for the treatment of exchange...

kenmore square north - loopnet · fenway cambridge treet...

wien2k- hardware/software

invited article electronic structure of solids with wien2k

s erwer obliczenio wy instytutu fizyki ap i p akiet do...

the band gap problem: the accuracy of the wien2k code...

improvement of the msr1a algorithm in the wien2k code

relativistic effects & non-collinear magnetism (wien2k / ...

methods available in wien2k for the treatment of exchange...

federal employees non-fehb - myuhc.com a form...2015...

25th annual meeting tuesday and wednesday, 5-6 december...

relativistic effects & non-collinear magnetism (wien2k /...

solid state calculations using wien2k

wien2k: an apw+lo program for calculating the properties...

localized electrons with wien2k

f. tran - wien2k · methods available in wien2k for the...

relativistic effects non-collinear magnetism...

optical properties with wien2k - pennsylvania state …...

introduction to the wien2k code

the all-electron gw method based on wien2k: implementation...