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# Density Functional Theory

## applied to the solid state

An introduction to VASP
Jeremie Zaffran
2
nd
year-MSc. (Nanochemistry)
zaffran.j@gmail.com
Supervisors: Pr. Leeor Kronik, Amir Natan (PhD) & Noa Marom(PhD)
Contents
I- DFT and its functionals
A. On the density functional theory
B. The exchange-correlation approximation
C. The functionals we used
II- VASP software
A. Generalities
B. Running calculations with VASP
C. Overview on the INCAR file parameters
III- Performances and restrictions of few density functionals
A. Presentation of the project
B. The process
C. Results
Conclusion
I- DFT and its functionals
I-DFT and its functionals
A- On the density functional theory
Why do we need DFT?
Ab initio calculations (no experimental parameter)
elec elec elec elec
E H + = +

Encountered problems
function of 3.N space variables
( )
N N N elec
z z y y x x ,..., , ,..., , ,...,
1 1 1
+
The wavefunction has no physical sense only its square is an observable
Very time-consuming!
I-DFT and its functionals
The basis
ext
universal
ee e e
V V T H

+ + =

Proper to the system
| |
ext
V N E E ,
0
=
{ }
ext
V N, is sufficient to define any chemical system
Which means
The DFT core: Hohenberg-Kohn Theorems (1964)
I-DFT and its functionals
1) The external potential is a unique functional of the ground state density
ext
V 0

{ } ( )
0 0 0
,

, E H V N
ext
+
(and all other properties)
2) The ground state energy will be reached if and only if one uses the ground state
density in the energy functional.
0

0
E
which means | | | |
0 0
, E E E
trial trial
= > Or | | ( )

E E min
0
=
Variational principle!
DFT key points
The electronic density becomes the fundamental variable!
Interest:
is only a function of 4 variables (x,y,z,s) and no more of 3N variables as with .
is an observable.
+

Any DFT algorithm should aim to reach only the ground state and no excited state!
The energy minimisation algorithms have to take care about two main constraints lying on the density:
must be N-representable, which means associated to an acceptable wave function :
square-integrable functions The Slater determinant is only an example of such a set!
must be V
ext
-representable, which means giving rise to a finite external potential.
Note that to this date we dont know what makes a density V
ext
-representable on the mathematical point of view.

## Levy constrained search scheme

I-DFT and its functionals
Expression of the energy functional and limitations of the Hohenberg-Kohn theorems
Feature of the system
Universal functional
| |
}
= dr V V
eN ext

HK
F ???? ( T is not a functional of the density, and E
ee
is not completely known)
| | | | | | | |

HK
F
ee ext
E T V E + + =
I-DFT and its functionals
Owing to the Kohn-Sham approach
| | | | | | | | | |
xc S ext
E J T V E + + + =

xc
S
ext
E
J
T
V
: External field (from the nuclei)
: Kinetic energy of an ideal system
: Columbic repulsion
: Exchange-correlation
Where
| | | | | | ( ) | | | | ( )
| | | |

ncl C
ee S xc
E T
J E T T E
+ =
+ =

ncl
C
S
E
T
T
T
: Kinetic energy of the real system
: Kinetic energy of the reference system
: Residual kinetic energy
: Non-classical energy
with
Nevertheless, what is ?... No one knows except from this un useful formalism
xc
E
xc
E must be approximated
I-DFT and its functionals
B-Exchange-correlation approximations
Classical and non classical effects due to the many-body interacting system.
Several ways to express it
Local Density Approximation (LDA):
Based on the homogeneous electrons gas model. Exchange-correlation density
functional is exactly known owing to the Thomas-Fermi model.
Application of the gradient operator on the previous model.
Meta-GGA: BB95
Application also of the laplacian operator.
Hybrid functional: HSE06, B3LYP
Introduction of an exact Hartree-Fock part in the Exchange functional.
GGA
C
GGA
X
HF
X xc
E E E E + + = %) 1 ( %
I-DFT and its functionals
C-The functionals we used
We assessed the performance of 3 GGAs
1. PBE (Pedrew-Burke-Ernzerhof)
2. PBE sol- devoted to the solid state
3. Rev PBE- devoted to the molecules
| | | | ( ) ( ) r r
3
. d s F E
X
unif
X X
}
= c | | ( ) | | ( ) r r
3 2
...d t E
unif
C C
}
+ + = | c
( ) ... 1 0
2
+ + = s s F
X

Enhancement factor:
Dimensionless
( )
3 / 4
3 / 1
2
3 2 t
V
= s
( )
6 / 7
6 / 1
2
3 4 t
V
= t
Exchange/Correlation energy per
particle in the free electron gas
model
I-DFT and its functionals
II- DFT and VASP software
II-DFT and VASP sofware
A- Generalities
Solid chemistry codes can be based on:
Atomic orbitals expansion
CRYSTAL
Plane waves (Bloch functions) expansion
VASP
II-DFT and VASP software
Overview on VASP calculations
Band structures calculations
Phonon dispersion
IR and Raman spectra
Molecular dynamics Simulated annealing
Bulk and surface calculations
To relax a crystalline structure
II-DFT and VASP software
Initially developed at the MIT by Payne, enhanced in the 90s by Hafner and
Furthmller at Vienna University and at Cambridge.
MPI parallelization in ~96 by Holender and Holender (UK)
Bloch waves approach calculations on the reciprocal space (using FFT-
algorithms)
Periodic boundaries conditions
extremely well convenient for crystals study, hardly efficient for single
molecules
Valence electrons treated explicitly, core electrons with pseudopotential
approximation (PAW method)
II-DFT and VASP software
The pseudopotential idea
Close to the atomic core, wave function has a chaotic behavior
To replace the chaotic wave
function by a smoother one and its
associated potential
Many methods to generate it:
Semi-empirical
Ultra-soft
Norm-conserving
Numerous interests:
Reduction of the electrons number
Reduction of the basis set
Enhancement of the calculation
time
II-DFT and VASP software
B-Running calculations with VASP
Main files
1. POTCAR- Pseudopotential (chemical species properties)
2. POSCAR- Lattice structure
3. KPOINTS- K-points mesh generation
4. INCAR- Central file
INPUTS
1. OUTCAR/OSZICAR
2. DOSCAR- density of states
3. WAVECAR- KS-orbitals
4. CONTCAR- Final ions positions if relaxation
5. CHGCAR- electronic density
6. CHG- electronic density for visualization
7. Vasprun.xml- for dos and band structure visualization
OUTPUTS
II-DFT and VASP software
Input files
POTCAR
Contains all the necessary information related to the treated
chemical specie
Plane wave basis set
Atomic mass
Total and valence electrons number
Proper to the each functional (LDA, GGA)
If several species
cat POTCAR_A POTCAR_B > POTCAR
In the same order they appear in the POSCAR!!!!
II-DFT and VASP software
Input files
POSCAR
Cubic BN
3.57
0.0 0.5 0.5
0.5 0.0 0.5
0.5 0.5 0.0
1 1
Direct
0.00 0.00 0.00
0.25 0.25 0.25
Comment line
Scaling factor, i.e lattice parameter
Lattice vectors
1 atom of B and one atom of N
Cartesian coordinates (either Reciprocal coord.)
Coordinates of B
Coordinates of N
II-DFT and VASP software
Note
The time demand increases with the cell size - even if the atoms number is
kept constant
Atomic species cell size
Li 13
Al 12
K 14
Cu, Rh, Pd 10
C 8
To simulate amorphous state or single molecules, take a big cell with plenty
of vacuumto prevent border effects
II-DFT and VASP software
Input files
KPOINTS
Several methods according to the expected property
k-points along high symmetry lines
10
Line-mode
Rec
0 0 0 ! gamma
0.5 0.5 0 ! X
0.5 0.5 0 ! X
0.5 0.75 0.25 ! W
0.5 0.75 0.25 ! W
0 0 0 ! gamma
Comment line
10 K-points along each line
Reciprocal space coord.
BAND STRUCTURE CALCULATION
II-DFT and VASP software
Input files
Automatic mesh
0
Monkhorst-Pack
4 4 4
0. 0. 0
Comment line
Automatic generation
Generation method
4 k-points on k
x
4x4x4 kpoints
KPOINTS
II-DFT and VASP software
C- Overview on INCAR file parameters
SYSTEM= Rhodium
NEDOS=300
ISMEAR=-5
SIGMA=0.05
ENCUT=500
IBRION=-1
! ICHARG=11
Comment line
Amount of flags, but all of them have default
values
Run out this tag
II-DFT and VASP software
ISMEAR, SIGMA: Occupancies wave function method convergence
method (depends on the system chemical nature)
ENCUT: Energy cutoff (~size basis set)
IBRION: Static calculation, ab-initio MD, relaxation algorithms (CG, SD)
ICHARG: To apply SCF on the charge density or not?
ISPIN: Is the system magnetic?
GGA: Which functional to use?
LHFCALC: Hartree-Fock calculations
AEXX/ALDAC: Hybrid functionals (VASP05)
The most used
III- Performances and restrictions of
few density functionals
III- Performances and restrictions of few density functionals
A-Presentation of the project
To assess the performance of 3 GGAs:
PBE
PBEsol solid state study
revPBE molecule study
Study already performed by Csonka in Physical Review B 79, 155107 (2009)
only on lattice parameter optimization
Objectives:
1. To reach a more important precision on lattice parameter
2. To assess their performance on band structure and density of
states calculation
B-The process
1. To optimize the number of K-points
2. To optimize ENCUT
3. To get the charge density
4. To deduce band structure and density of states
III- Performances and restrictions of few density functionals
K-points optimization
Ge- PBE
Convergence at 23x23x23 k-points
Objective:
To get the convergence with
the smallest set of k-points
GaAs- PBE
Convergence at 21x21x21 k-points
III- Performances and restrictions of few density functionals
ENCUT optimization
Objective:
To reach the harmonic
approximation (close to the
equilibrium) with the smallest
Energy Cutoff
III- Performances and restrictions of few density functionals
C-Results
On the lattice parameter
III- Performances and restrictions of few density functionals
On the band structure
LDA calculation: Natan et al., PRB 78, 075109 (2008)
III- Performances and restrictions of few density functionals
On the band structure
III- Performances and restrictions of few density functionals
On the bandgap assessment
III- Performances and restrictions of few density functionals
Greatest discrepancies
The closest to the experiment
Conclusion
Excellent results for lattice parameter optimization
DFT is not a suitable method for band-gap calculation
DFT only deals with the ground state
However, we can expect that more accurate functionals as Hybrid one could
better approach the gap.
Other methods are more appropriate like Time-Dependent-DFT or post-HF
methods (CI)
Very time consuming!!!
Any functional has to be adapted relatively to the physico-chemical nature of
the system (metal, semiconductor)and for a given property!