TMCSIII: Jan 2012, Leeds

PSEUDOPOTENTIALS FOR BAND

STRUCTURE CALCULATIONS

Rita Magri
Physics Department, University of Modena and
Reggio Emilia, Modena, Italy
CNR-Nano -S3 , Modena, Italy
OUTLINE

 Evolution of the Pseudopotential Concept

 First-Principles Pseudopotentials

 Empirical Pseudopotential Method

 Construction, Use and Results

EVOLUTION OF THE
PSEUDOPOTENTIAL CONCEPT

• The Beginning
- OPW formalism - Herring , Phys. Rev. 57, 1169 (1940)
- Phillips and Kleinman, Phys. Rev. 116, 287 (1959)
- Cohen and Heine, Phys. Rev. 122, 1821 (1961)

• Empirical Pseudopotentials
- Cohen and Bergstresser, Phys. Rev. 141, 789 (1966)
- Chelikowsky and Cohen, Phys. Rev. B 14, 556 (1976)

• Model Pseudopotentials
- Abarenkov and Heine, Phil. Mag. 12, 529 (1965)
WHY PSEUDOPOTENTIALS?
 The fundamental idea of
a pseudopotential is to
replace one problem with
another. (R. Martin,
All-electron (true)“Electronic Structure”,
Wave function Cambridge)

 Replace the strong

Coulomb potential of the
nucleus and tightly
bound core electrons by
an effective ionic
All-electron (true) Figura potential acting on the
potential valence electrons.
 THE GENESIS OF THE PSEUPODOTENTIAL
CONCEPT
Reciprocal Space Representation
 Taking the Fourier transforms of the periodic part of the Bloch
function uk(r) and the periodic crystal potential V(r)
(which become series in G) and substituting into the Schrödinger
Equation we obtain:

  
  i ( k  G )  r
ik  r
 k (r )  e u k (r ) 
 
 u k (G ) e
G

 2   2      
 k  G  E ( k )  u k (G )  

V ( G  G )u k (G )  0
 2m  G

Slowly
Convergent uk and V
 HOW TO CALCULATE CRYSTAL BLOCH
FUNCTIONS FOR VALENCE ELECTRONS?
• The first problem is that the crystal potential V is a highly
varying function of real space. Also wavefunctions are expected
to change a lot, with atomic-like behavior near the nuclei and a
more plane wave-like behavior in the interstitial regions, where
V is weaker.

• It is not possible to express uk (r) as a simple superposition of

plane-waves. Too many would be required!!!

> 105 plane waves

per atom!! Core Wiggles
 FIRST STEP
 The lower lying bands come from the atomic core levels,
while the electrons in higher bands feel a weaker potential
(screened by the core electrons).
• The main idea is to divide the bands into two groups,
in the first group are the low-lying bands of core electrons,
in the second group are the valence and conduction bands.

Valence states
Large
Energy
difference

Core states
Atomic C (Z = 6) Atomic Cu (Z = 29)
 OPW FORMALISM (HERRING, 1940)
• We assume the narrow lower bands are unchanged by
the atom environment (Frozen Core
Approximation): so we can approximate these
states with the core states of the free atom or other
appropriately chosen localized functions φj.
• We are interested in describing valence electron
bands (core electrons are chemically inert)
  Core
True   (r )   n,k (r )    j  n,k  j

States
valence n ,k
j
function
Smooth Localized function
function

 It can be shown that ψn,k is orthogonal to all φj

 THE PSEUDOPOTENTIAL (PROTOTYPE PSP)
• We now insert the expression
 
 n , k ( r )   n , k ( r )    j  n , k  j
 
j
into the Schrödinger equation and obtain:
 
Hˆ  n    j  n Hˆ  j  En (k )  n    j  n  j 
j  j 
 
 
 
Hˆ 0  V (r )  n   En (k )  E j  j  j  n  En (k )  n
j
Nuclear potentials
• an equation for the smooth function χ. We
have an effective potential:
 
 
 
V ps (r ,  j )  V (r )   En (k )  E j   j (r )  j
j
PROPERTIES OF PSEUDOPOTENTIAL
 >0
 
V ps (r ,  j )  V (r )     
En ( k )  E j   j ( r )  j
j

Attractive Repulsive
long-ranged short-ranged
 Vps is a much weaker potential than V: the attractive and
repulsive parts partly compensate in the core region
(Cancellation Theorem, Cohen and Heine, 1961)
• Vps depends generally on the angular momentum φj = φlmj
and is a non-local energy-dependent integral
operator.
 No effect if there are no core functions with angular
momentum l. The true valence function has no nodes.
 WHAT IS MORE IMPORTANT ….
 We got rid of the core states/electrons. Valence electrons
feel a “pseudopotential “ weak in the core region
instead of the nucleus + core electrons

SAME EFFECTS
ON THE
VALENCE ELECTRONS

Core Electrons Pseudo Core

Valence Electron
THE PSEUDOFUNCTION FOR THE
VALENCE ELECTRON
• χ being slowly varying can be approximated by a
few terms of a superposition of plane waves.

Core region

Bonding region
PROPERTIES OF THE SMOOTH
PSEUDOFUNCTION

• χ is not the valence electron wavefunction but only its

smooth part (no wiggles in the core).
• The equation for χ has the same eigenvalues En(k) for
the valence electrons as the original Hamiltonian.
• χ is not uniquely defined.

• The “pseudofunction” χn,k:

 n , k  n , k  1    j  n , k
2
Norm is not unity!
j

 Note: if we know the smooth “pseudofunction” we

can always build the corresponding true valence
function.
MODEL PSEUDOPOTENTIALS,
EMPIRICAL PSEUDOPOTENTIALS,
FIRST-PRINCIPLES PSEUDOPOTENTIALS
 In practice the expression for Vps is
approximated.
 Vps can be built to satisfy our needs, for
example we can require it to be the smoothest
and weakest possible and maintaining the
same scattering properties of the core potential
on the valence electrons (ab-initio approaches),
or reproduce some measured quantities
(empirical approaches)
TERMINOLOGY: LOCAL PSEUDOPOTENTIAL
 The pseudopotential can be local, semilocal, non-
local.
 Please note ALL the pseudopotentials are spherically
symmetric. (thus given on a radial mesh)

 LOCAL  s, p, d electrons
all feel the same
Pseudopotential potential
(the less accurate)

 EMPIRICAL and
MODEL
VˆL  VL (r ) Pseudopotentials
TERMINOLOGY: SEMILOCAL PSEUDOPOTENTIAL

 SEMILOCAL  It is non-local in the angular

variables, local in the radial
Pseudopotential variable Pseudo
Wave
VˆSL   Ylm Vl (r ) Ylm functions
lm Spherical
harmonics d

p
 s, p, d electrons
feel different
potentials

Mo – from Haman, Schluter and Chang

PRL 43, 1494 (1979)
TERMINOLOGY: NON-LOCAL PSEUDOPOTENTIAL

 NON LOCAL SEPARABLE

Pseudopotential
 Fully non local in angles θ
VˆNL  
 lm El  lm
lm
and φ AND radius r

Functions of r, θ, φ

 In position representation VNL (r , r )
 Note: this PSP form is closer to the prototype PSP
 THE L-DEPENDENT TERMS ARE SHORT-RANGED
 The l-dependent terms of V are different only inside the
core region (radius rc). A common long-ranged local
potential Vloc (r) is subtracted
 In this way the semilocal, non-local terms of the
pseudopotential are zero outside rc. r
c

Vˆ ps  Vlocps (r )    lm El  lm
lm

Z ion e Vanishes
V ps
loc 
r outside
at large r rc
MODEL PSEUDOPOTENTIALS
 The model potential of Abarenkov and Heine (1965)
 The core is a black box. Any core potential which
yields the correct logarihmic derivative at rc is OK.

Al

Usually Al(E) is often a constant

value
fitted to reproduce the
atomic eigenvalues and data
Al
FROM THE IONIC (OR ATOMIC)
PSEUDOPOTENTIAL TO THE CRYSTAL
POTENTIAL
 Valence electrons move in the crystal potential
 Pseudopotentials describe the interaction of the valence
electrons with a single ionic core.
 In the crystal the valence electrons interact one each
other
 We have screened pseudopotentials (usually in
empirical calculations) or ionic (bare)
pseudopotentials (unscreened, usually in first-
principles calculations).

 The crystal potential is built as a superposition of atomic

pseudopotentials
 CRYSTAL POTENTIAL
 Let’s suppose the pseudopotential is local, then it can
be written simply as Vα(r). The electron Hamiltonian
is:
(AB-INITIO) Hˆ  Tˆ  VˆHxc  Vˆion or Hˆ  Tˆ  Vˆion
screened
(EPM)

    α is the ion kind

Vion (r ) 
 , R ,
V (r  R    )
R is the lattice vector
τα is the basis vector
 Whose Fourier expansion is:

     
Vion (r )  

e  e
iG  r  iG  
V (G ) G is a reciprocal
G   vector

Structure Form
Factor Sα(G) Factor
 EXAMPLE: GAAS BULK

 Two atoms in the unit cell:

Ga in τGa = τ = (1/8,1/8,1/8)a, As in τAs = -(1/8, 1/8,1/8)a =-
τ, we obtain:

 

 
  

 


V (r )  

iGr
e cos(G  ) VAs (G)  VGa (G)  i  sen(G  ) VAs (G)  VGa (G)
G

VS(G) VA(G)
 And solve:
 2   2      
 k  G  E ( k )  u k (G )  

V ( G  G )u k (G )  0
 2m  G

 The form factors are treated as adjustable parameters

(empirical approach). Only those corresponding to few
G vectors are needed.
Cohen and Phys. Rev.
Bergstresser 141, 789-796
(1966)
 Using the empirical approach the band
structures, reflectivity spectra and photoemission
spectra of bulk IV, III-V, and II-VI
semiconductors were calculated (Cohen and
Chelikowsky “Electronic Structure and Optical
Properties of Semiconductors”, Ed. Springer)

 It is difficult to apply this method for systems

with hundreds or thousands of atoms per unit
cell because the fitting parameters (the form
factors for each G-shell) would become too many!

-New Atomistic Pseudopotentials (AEPM)

FORM FACTORS FOR SEMI-LOCAL PSP
 If the pseudopotential is semi-local still we have
the structure factor and the form factor is more
complicated:
    
V (k , G, G)  V ,loc 
,loc (G  G ) 

    
 l
P
l
(cos  )  l l
V
0
( r ) j ( k  G r ) jl ( k  G  r ) r 2
dr

  
   
with: k  G  k  G
cos      
k  G k  G
 It depends on k and requires a double loop over the G
vectors or in real space a radial integral for each pair of
basis functions  computationally very expensive!
NON-LOCAL (SEPARABLE) PSPS DO IT BETTER
 Non-local pseudopotentials make the
computation of the Hamiltonian matrix elements
less expensive. Instead of
    
Pl (cos  )  Vl (r ) jl ( k  G r ) jl ( k  G r )r dr
 2
0

 We have:
     
Pl (cos  )   l (r ) jl ( k  G r )r dr   l (r ) jl ( k  G r )r 2 dr
2
0 0

 Factorized into a product of integrals for each basis

function separately, in plane-wave calculations only
single loops over G are involved.
 HOW TO GENERATE AN ATOMIC
PSEUDOPOTENTIAL

 Pseudopotentials for first-principles

calculations
 Unscreened (bare) pseudopotential
(ionic psp)
 Extracted from an all-electron
calculation on the free atom.

 Pseudopotentials for semiempirical

calculations
 Extracted fitting experimental data of
(one or more) compounds containing
the atom.
 It is assumed to be screened.
PSEUDOPOTENTIALS FOR FIRST-
PRINCIPLES CALCULATIONS

Main steps in development

 Hamann, Schlüter, and Chang, PRL 43, 1494 (1979) – Norm-

Conserving Pseudopotentials
 Kleinman and Bylander, PRL 48, 1425 (1982) – Separable
Pseudopotentials
 Louie, Froyen, and Cohen, PRB 26, 1738 (1982) – Non linear
core correction
 Vanderbilt, PRB (RC) 41, 7892 (1990) – Ultrasoft
Pseudopotentials
 Blöchl, PRB (RC) 41, 5414 (1990) – Generalized Separable
Pseudopotentials
 Blöchl, PRB 50, 17953 (1994) - PAW
 REQUIREMENS FOR CONSTRUCTING A GOOD
NORM-CONSERVING PSEUDOPOTENTIAL

 Hamann et al. PRL 43, 1494 (1979)

 Choose an atomic reference configuration Example: Si 3s2 3p2

 Use an atomic code to calculate the all-electron valence
wavefunctions (AE).

 Impose that the

pseudo-wavefunction
(PS) agrees with the
(AE) wave-function
beyond a chosen cutoff
radius rc (l-dependent)
 Also the l-channel pseudo-potential (PS) has to
agree with the AE potential for r > rc.

 1 d 2 l (l  1)  nlm
 2
 2
 VAE (r )   nl  AE (r )  0
scr .

 2m dr 2mr 
 1 d 2 l (l  1)  nlm
 2
 2
 VPS (r )   l  PS (r )  0
scr .

 2m dr 2mr 
for the same eigenvalue εnl = εl
NORM-CONSERVATION REQUIREMENT
 The integrals from 0 to rc of the real and pseudo
charge densities agree for each valence state.
rc rc
rc
 dr   r 
l 2 nlm 2
r 
2
PS
2
AE dr
0 0

The charge contained

in this region is the
same for AE and PS
wave-functions
SCATTERING PROPERTIES

 1 d 2 l (l  1)  nlm
 2
 2
 VAE (r )   nl  AE (r )  0
scr .

 2m dr 2mr 
 1 d 2 l (l  1)  nlm
 2
 2
 VPS (r )   l  PS (r )  0
scr .

 2m dr 2mr 

 . By construction, we know that at energy ε = εnl, the

solution ψPS(r ) coincides with the ψAE(r ) for r > rc.
But what about other energies? The transferability
of the pseudopotential depends on the fact that ψPS(r )
reproduces ψAE(r ) over a certain range of energies
about εnl. We are interested in the energy range of
valence bands in solid.
  The logarithmic derivatives of the real and pseudo
wave function and their first energy derivatives
agree for r > rc.
Logarithmic
derivative
 l( , r ) d
Dl ( , r )  r  r ln l ( , r )
 l ( , r ) dr

 The first energy d

derivative of the Dl ( , r )
logarithmic d
derivatives of the all-
electron and pseudo
wave-functions agrees
at rc, and therefore for
all r > rc.
SCATTERING PROPERTIES

 The fundamental advance of Hamann, Schlüter

and Chang, 1979, is to have shown that:
If norm conservation is imposed, then pseudo
Dl(ε,r) matches all-electron Dl(ε,r) to second
order in (ε –εl)

 This means that the norm-conserving

pseudopotential has the same scattering phase
shifts as the all-electron atom to linear order in
energy around the chosen energy εl.

 These properties however leaves plenty of

freedom in the form of the pseudopotential and in
its construction.
STEPS FOR PSEUDOPOTENTIAL
CONSTRUCTION
 Step 1: choose a reference configuration
F : (1s)2 (2s)2(2p)5
Si: (1s)2(2s)2(2p)6 (3s)2(3p)2
 Step 2: solve the all-electron problem:
VAE(r),ψAE,nl(r)
 Step 3: construct the pseudo wavefunction that satifies
rules (nodeless, matching to AE wavefunction, norm-
conservation, etc)
 Step 4: Invert the Schrödinger equation to get VPS,l(r)
which is a screened potential
 Step 5: Unscreening the potential to obtain the bare
VPS,l,ion
PSEUDOPOTENTIAL GENERATION
VERY IMPORTANT STEP: THE PSEUDO
TEST
(1) Tests on excited configurations”

Example: Reference configuration for Si [core]s2p2
we compare AE and PS results for other configurations:
[core]sp3
[core] s2p1 ….. and many others

 We compare
- Total energies
- Energy Eigenvalues
- Logarithmic derivatives

 Then calculate small (well-known) systems and check

…..
OPTIMIZATION OF A PSEUDOPOTENTIAL
 Pseudopotentials are optimized with regard to:
1. Accuracy and trasferability – leads to
choose small cutoff radius rc and harder
pseudopotentials
2. Smoothness – leads to choose a larger cutoff
radius rc and softer pseudopotentials

Different
Authors
have
Proposed
different
Recipes
CONSTRUCTION RECIPES FOR SMOOTH
AND ACCURATE NORM-CONSERVING PSPS
 Bachelet, Hamann, Schlüter, PRB 26, 4199 (1982)

 Vanderbilt, PRB 32, 8412 (1985)

 Kerker, J. Phys. C 13,L189 (1980)

 Troullier and Martins, PRB 43, 1993 (1991)

 Rappe, Rabe, Kaxiras, and Joannopoulos, PRB 41, 1227 (1990)

 ……….. Cu
Troullier-Martins Kerker HSC Vanderbilt

From Troullier and Martins, PRB 43, 1993 (1991)

UNSCREENING THE PSEUDOPOTENTIAL

 The inversion of the Schrödinger equation gives the

screened pseudopotential. We need to unscreen it.
 To unscreen:
nPS (r )   f l  (r )
2
l
PS
Pseudo valence charge density

(r )  VH [nPS ], r   Vxc ([nPS ], r )

l
PS
V Hxc
PS
Vion ,l ( r )  V PS
scr .,l ( r )  V PS
Hxc ( r )

 However, Vxc is a non-linear functional of n so it is ambiguous

to separate the effects of core and valence charge if there is a
significant overlap of the two densities.
 This leads to errors and reduced transferability.
NON-LINEAR
CORE CORRECTIONS
Vxc ([ntotal ( PS  core ) ], r )
IMPROVEMENTS ON THE METHOD: SEPARABLE
PSEUDOPOTENTIALS

 We separate the semi-local pseudopotential in a long-

range local part and one short-range l-dependent part
PS
Vion (r )  Vlocal
PS
(r )   l , m Vl PS (r ) l , m
lm

 Separable Pseudopotentials (Kleinman-Bylander

Trasform) 1982
 PS
 V PS
 V PS
 PS

VˆNL  V local ( r )  
PS lm l l lm
For each l-channel
l ,m  lmPS  V l PS  lmPS

VNL acts on the reference state ψlm as the

semilocal pseudopotential ΔVl
 Possible presence of bound ghost states at lower
energies requires some care.
 IMPROVEMENTS ON THE METHOD: ULTRA-
SOFT PSEUDOPOTENTIALS
 First-row elements have valence states with angular
momentum l without l core state. Already nodeless!
PS O: 1s2 2s2 2p4 no p states in core
AE core valence

O 2p wavefunction
NORM-CONSERVATION makes PS  AE

Highly localized states in first

row and transition-metal atoms

New “core” Difficult convergence in a

Radius for UltraSoft plane wave basis
 D. Vanderbilt, Phys. Rev. B 41, 7892 (1990)

 Release the norm conservation criteria to obtain

smoother pseudo wave functions. This is done by
splitting the pseudo wave functions into two parts:
1. The ultrasoft valence wave function that do not
fulfill the norm conservation criteria:
 (r )
US
i
2. Plus a core augmentation charge (charge deficit
in the core region):
Qij (r )   i, AE (r ) jAE (r )  i,US (r ) US
j (r )

 The Ultra-Soft Pseudopotential takes the NL form

 US
V  Vlocal (r )   Dij  i  j  i   i  T  Vloc  i
ij
 An overlap operator S is introduced:

S  1   Qij  i  j
ij

   2 
n(r )    i (r )   Qlk (r )  i  l  k i 
i  lk 
0 in case of norm-conservation

 Main Properties:
1 Changed orthonormalization: i Sˆ  j   i , j
2 Generalized eigenvalue problem to be solved
( Hˆ   nk Sˆ )  nk  0
2 The NL Pseudopotential is updated during the
iterative procedure
  
D It
mn  D   dr VHxc (r )Qmn (r )
0
mn
A PSEUDOPOTENTIAL FOR ALL SEASONS
 Many different PSPs and Pseudo Generator
Codes provided in packages:

Plane-waves pseudopotential codes

http://www.quantum-espresso.org/pseudo.php
On-The-Fly Pseudopotential Generation in CASTEP -
a 164 kB pdf tutorial.

http://cms.mpi.univie.ac.at/vasp/vasp/

http://www.abinit.org/downloads/atomic-data-files
 http://www.quantum-espresso.org/pseudo.php

PSEUDO-ELEMENT TABLES
 Name: Oxygen
Symbol: O
Atomic number: 8
Atomic configuration: [He] 2s2 2p4
Atomic mass: 15.9994 (3)
Available pseudopotentials:
O.pz-mt.UPF (details)
Perdew-Zunger (LDA) exch-corr Martins-Troullier
O.blyp-van_ak.UPF (details)
Becke-Lee-Yang-Parr (BLYP) exch-corr
Vanderbilt ultrasoft author: ak
O.pbe-van_gipaw.UPF (details) And many other…….
Perdew-Burke-Ernzerhof (PBE) exch-corr
Vanderbilt ultrasoft author: gipaw
O.blyp-mt.UPF (details)
Becke-Lee-Yang-Parr (BLYP) exch-corr Martins-Troullier
O.pz-kjpaw.UPF (details)
Perdew-Zunger (LDA) exch-corr Projector Augmented
Waves (Kresse-Joubert paper)
O.pbe-van_ak.UPF (details)
Perdew-Burke-Ernzerhof (PBE) exch-corr Vanderbilt
ultrasoft author: ak
O.pbe-rrkjus.UPF (details)
Perdew-Burke-Ernzerhof (PBE) exch-corr Rabe Rappe
Kaxiras Joannopoulos (ultrasoft)
PSEUDOPOTENTIALS FOR SEMIEMPIRICAL
CALCULATIONS

Main steps in development

 Chelikowsky and Cohen, PRB 14, 556 (1976)

Atomistic Empirical Pseudopotential

 Mader and Zunger, PRB 50, 17393 (1994) –

 Wang and Zunger, PRB 51, 17398 (1995) – LDA derived
semiempirical pseudopotentials
LDA-DERIVED EMPRICAL PSEUDOPOTENTIALS

 Problems with first-principles methods

1. Difficult to apply to systems with thousands-
million atoms (nanostructured materials)

2. Problem with excited states: the band gap is

often severely understimated  comparison
with experiments (spectroscopies) not goood

Transferable screened pseudopotentials

The idea: reproduce experimentally determined band
energies, optical spectra, etc, and at the same time, LDA-
quality wavefunctions and related quantities.
SEPM FROM LDA CALCULATIONS

1. LDA SLDA
Form factors 

Local Potential
- Calculate LDA for structure  VLDA (G )
Vloc+VHxc
- Spherical Average of the Screened Local Potential
   , 
V 
LDA (G )   S (G )vSLDA ( G )
 ,


  ,
- Structural average vSLDA (r )  vSLDA (r )


 
-The points v SLDA (G ) vs G are fitted by the continous
function :
N
2. SLDA SEPM

- Only the Coefficients CSLDA are adjusted to fit

the experimental or quasiparticle calculated
excitation properties
 Unlike standard EPM, which produces only discrete
form factors and is hence suitable only for a
particular crystal structure and lattice constant, the
new SEPM or AEPM can be used for different
structures and volumes with good transferability.
The form factors for each particular structure
are extracted from a “Universal” continous
function of q
N ( 4 , 5, 6 )
q 2  a1
  cn ( q bn )
v ( q )  a 0
2
v (q)  a n e or  a 3 q 2
n 1 a e
2 1
PROPERTIES OF AEPMS

• Good band structure

• Accurate effective masses

• Accurate band gaps

• Good elastic properties

(Bulk modulus, deformation potentials)

• Transferable

• Low Energy cut-off (~5 Ryd)

• Simple analytic form (few parameters)

AVAILABLE ATOMISTIC EMPIRICAL
PSEUDOPOTENTIALS

Only certain
combinations
are available
(IV, III-V, II-
VI)
AN EXAMPLE: THE INAS/GASB SYSTEM

 Broken Gap System

 Semiconductor because of the e1

and h1 confinement

 Possibility of tuning the band

gap between 0 ↔ 400 meV

 Type II: short periods SLs to

increase the radiative
ricombination efficiency
 GaAs InAs GaAs

CA

As As
G In In
G
a
a

The single (001)

interface has C2v
symmetry As Sb
Ga In G
In
NCA a
GaSb GaSb
InAs
IN-PLANE POLARIZATION ANISOTROPY
e h 
I ( p [1 1 0 ])
e h   1
I ( p [ 1 1 0 ])

InAs/AlSb
superlattice
Y=[-110]
X=[110]
Fuchs et al. in
“Antimonide-Related
Strained-Layer
Heterostructures”

Wavenumber (cm-1)
 ATOMISTIC EMPIRICAL PSEUDOPOTENTIAL
ELECTRONIC STRUCTURE
• Solve the Schrödinger equation FULLY ATOMISTICALLY,

  2
 plane wave
   v r  R n  (r )   (r ) expansion
 2m n   of ψ(r)

each atom strain

individually minimizing
described atomic positions

Folded
• not self-consistent spectrum
method
• no LDA errors

The spectrum at the left is the original

spectrum of H. The spectrum at the right is
the folded spectrum of (H-E_ref)^2
 FORM FACTORS
• v(q) continous function of q

v (r )  e v (| q |)1  vn  vn ( )  a4 Tr( )

i q( r )

q 2  a1
v ( q )  a 0  a 3 q 2
a e
2 1
 Parameters fit to reproduce:
1. Gaps Eg and effective masses m*
2. Hydrostatic ag and for ALL 4
biaxial b deformation potentials binaries
3. Band offsets and spin-orbit splitting so
4. LDA-predicted single band edge
deformation potentials av, ac
FIT: RESULTS
 HANDLING OF BIAXIAL STRAIN
• Explicit strain dependence in v(q,)
with  v n  (  )  a 4 Tr (  )
EPM

LAPW

 IF specific offsets
 IF specific bonds
 CRYSTAL POTENTIAL FROM A
SUPERPOSITION OF ATOMIC POTENTIALS

Interfaces or n 4n
vIn (Asn Sb 4n )  vIn (InAs)  vIn (InSb)
Disorder 4 n
FIRST HEAVY-HOLE CHARGE DENSITY
The method predicts the positive band bowings parameters
of the ternary alloys in agreement with experiment!
 RESULTS FOR THE (INAS)6/(GASB)M AND
(INAS)8/(GASB)N SUPERLATTICES

Eg

with increasing n
CORRECT TREND!
(InAs)8/(GaSb)n

Number of GaSb monolayers n

OVERLAP OF THE ELECTRON STATES

InAs GaSb
LONG-PERIOD INAS/GASB SLS

 (InAs)46(GaSb)14
MORE TO BE SEEN FRIDAY MORNING ……

THANK YOU FOR YOUR ATTENTION

• If we choose a plane wave for χn,k we call the ψnk
an OPW (orthogonalized plane wave)
 1  1 q  r  
 OPW

q (r )  e
V 
   j q  j  OPW
j 

• OPWs were used as basis functions for expansion:


 n,k (r )    i  qOPW
,i
i

 Dependence on l,m
 j  l ,m, j (r )
 
 nl ,,mk ( r )   n , k ( r )    l , m , j  n , k  l , m , j
j