Running a DFT calculation in

VASP
ICME Fall 2012
Laalitha Liyanage
lsiliyanage@gmail.com

Codes

Density Funtional Theory

Hohenberg-Kohn theorems

Energy of the system is a unique functional of the

charge density
The correct ground state charge density minimizes the
energy functional and the resulting energy is the
ground state energy.

Exchange-Correlation functional:unknown
Approximations: LDA, GGA (PW91, PBE)

Kohn-Sham scheme

Map interacting system to non-interacting system

Well-converged calculation
Choose XC functional

Accuracy: LDA < GGA < Hybrid

k-points in Brillouin zone

Do k-point convergence

Accuracy increases with no. of k-points

For metals

Choose a smearing technique

Tetrahedron method good for very accurate total

energy calculations.
Gaussian, Methfessel-Paxton etc. good for ionic
and geometric relaxations

Energy cutoff

Controls completeness of planewave basis

set

Pseudopotentials

Replaces nucleus and core electrons with

fixed effective potential

What is VASP?
One of the software packages that uses DFT to solve the
quantum problem for materials
Uses periodic boundary conditions
Uses pseudopotential method
with a plane waves basis set
Can model systems with maximum
no. of atoms in the range of 100-200
Commercial software package ~$5000
Manual http://cms.mpi.univie.ac.at/vasp/vasp/PREC_tag.html

Other DFT packages (public license)

Quantum espresso (www.quantum-espresso.org)

Abinit( www.abinit.org)
Siesta (http://icmab.cat/leem/siesta/)

VASP input files

INCAR

User specified parameters that define the calculation

Global break condition, Energy cutoff, Smearing, Ionic and
geometric relaxation parameters

POSCAR

Specifies the periodic simulation cell

Information regarding geometry of the system

POTCAR

Pseudopotential (PP) file

Information on PP and XC functional

KPOINTS

Defines k-point mesh

Our system
Al
4 atoms, fcc structure
Translational lattice vectors
a1 = (4.0; 0.0; 0.0)
a2 = (0.0; 4.0; 0.0)
a3 = (0.0; 0.0; 4.0)

Basis vectors

0.0; 0.0; 0.0

0.5; 0.0; 0.5
0.5; 0.5; 0.0
0.0; 0.5; 0.5

POTCAR file with LDA XC

For all elements VASP provides PP files in different flavors

US-PP, PAW-LDA, PAW-GGA, PAW-PBE

If multiple species of atoms are in the system

Concatenate the same type of POTCAR files to make a single POTCAR file
E.g. cat POTCAR_Al POTCAR_Mg >> POTCAR

The order of the POTCAR types should correspond to the ordering of atoms
in POSCAR

POSCAR file

In Direct coordinates the positions of atoms are given as a fraction of

translational lattice vectors.

In Cartesian coordinates position of atoms is given in global coordinates.

Universal scaling factor scales the volume of the unit cell

If negative value is given then it is taken as the volume of the unit cell.

Order of atom types in POSCAR should be same with POTCAR

INCAR file
Minimal setup

ENCUT : Controls the no.

of plane waves in the
basis set
Default: ENCUT=Largest
ENMAX of POTCAR file
Best if convergence test
could be done

PREC : Controls the

overall precision of the
calculation
Default: Normal Standard
calculation
are sufficiently accurate with errors
less than 1 meV/atom

Low quick and dirty

calculations
Accurate High accuracy
calculations

For geometric relaxations

(changing cell size) set
ENCUT=1.3*ENMAXlargest

LREAL: use of
reciprocal/real space

Default: .False. uses in

reciprocal space
AUTO recommended for
systems more than 20
atoms. uses real space

ISMEAR

Default: 1 MethfesselPaxton
-5: Tetrahedron method

KPOINTS file
For Al bulk system

For Al single atom

k- point grid should be inversely propotional to the ratio of

lattice vectors (else it will give rise to errors)
E.g. If the lattice vectors are a1=3 a2=9 a3=21 then k-point grid
should be 7:3:1 ratio

Comments on k-points and smearing

Smearing

Guidelines for ISMEAR

For semiconductors or insulators always use tetrahedron method

(ISMEAR=-5) or if cell is too large use Gaussian smearing
(ISMEAR=0)
For relaxations in metals always use ISMEAR=1
Never use ISMEAR > 0 for insulators and semiconductors.

For very accurate total energy calculations (no relaxations in

metals) use the tetrahedron method (ISMEAR=-5).

k- point convergence

recommended to use even meshes (e.g. 8 8 8 ) for up to

=8
After that odd meshes are more efficient (e.g. 11 11 11)

http://cms.mpi.univie.ac.at/vasp/vasp/Automatic_k_mesh_generation.html
http://cms.mpi.univie.ac.at/vasp/vasp/Number_k_points_method_smearing.html
#im-smear

Standard output of a VASP run: PREC=N

N iteration count
E Total energy
dE change of total
energy

ncg no. of evaluations of the

Hamiltonian acting on WF
rms approximate error in WF
rms(c) difference between
input and output
charge density

Standard output of a VASP run: PREC=A

No wrap-around errors
Energy difference ~ 0.00001eV = 0.01meV
Therefore PREC=Normal with EDIFF=1e-04 is accurate enough.
Data from stdout are written to OSZICAR file as well.
http://cms.mpi.univie.ac.at/vasp/vasp/stdout_OSZICAR_file.html

OUTPUT files
CONTCAR
Contains position of the system after the calculation
has completed

OSZICAR
Contains data of electronic steps and ionic steps

OUTCAR
Complete output of run including input file data.

CHGCAR
Charge density of system after run

Bulk Relaxations: Setup

ISIF tag

determines which degrees of freedom

(ions, cell volume, cell shape) are allowed
to change.
To only optimize ionic positions with in
the cell do ISIF=2
To perform cell volume and cell shape
optimization do ISIF=2

NSW tag: Specifies the maximum no. of

ionic steps
Default NSW = 0

Since Al is metallic
Use ISMEAR = 1 for
IBRION tag: determines how the ions are
relaxation run
updated and moved.
If away from minimum use IBRION = 2
ENCUT is increased to
(Conjugate -gradient)
1.3*ENMAX to
If close to minimum use IBRION=1 (quasiaccommodate cell volume
newton)
change.
http://cms.mpi.univie.ac.at/vasp/vasp/IBRI
ON_tag_NFREE_tag.html

Bulk relaxation:Procedure
1. Using the relaxation setup INCAR do the first run
with ISMEAR=1 (since metallic) and ISIF=2/3

2. Next copy CONTCAR to POSCAR, clear output files

(use cleanvaspfiles) and run again
For ISIF=2 second step is unnecessary

3. Final step: switch on tetrahedron method

(ISMEAR=-5) to get very accurate energies

NEVER use energies from a relaxation run if volume

change is allowed.

http://cms.mpi.univie.ac.at/vasp/vasp/Accurate_bul
k_relaxations_with_internal_parameters_one.html

Volumetric relaxation procedure

Best method is to use do ionic relaxations (ISIF=2)
at different volumes and plot energy vs volume
curve.
Fit to equation of state and obtain equilibrium volume
and energy
evfitprogram offers several equation of state
equations which can be used for fitting purposes.

At the end of relaxation (ISIF =2/3) if converged

to parameters specified stdout will say

Automated Energy-Volume curve

Shell script
Uses lattice parameters from 3.5
to 4.5 ~ only 10 points
More points will increase
accuracy

Extracts

Final volume/ion
Energy/atom
Time for calculation

Makes 2 output files (2 columns)

Energy/ion for each lattice
parameter
Energy/ion for each volume/ion

Calculation at each fixed volume

could be static or only ionic
relaxations.

Curve fitting

Using evfit program we fit the

data to

Murnaghans equation of state

From the fitting we derive

Equilibrium lattice constant, bulk

modulus, and energy per atom.

Automated k-point convergence test

EV generation script is called for

different k-point grids
4x4x4, 8x8x8 and 11x11x11

At each fixed volume static

calculation is done
Total cpu time for these grids is
recorded

From 4x4x4 grid to 11x11x11 grid the time

taken quadruples
Energy difference is
From 4x4x4 to 8x8x8 ~50 meV
Form 8x8x8 to 11x11x1 ~ 6 meV

pbs script
For RAPTOR

To submit jobs to TALON or

RAPTOR you need a pbs
command script
Make sure that total no. of

processors you request is used

in your mpirun command

For TALON

mpirun np <nodes x ppn>

When doing calculations over

20 atoms use cluster

Surface energy calculations

First to very accurate bulk energy calculation
Do k-point convergence to ~< 1meV

if you want to calculate surface energies within

meV you should probably
increase the k-mesh till your energy is converged to 1 meV -VASP

Do Volumetric and ionic optimizations to a high degree

(PREC=Accurate, EDIFF=1e-06)

Next Setup surface calculation

Start with a system that has at least 5 layers of atoms and 5 layers of
vacuum.

Good rule of thumb: make system big enough that surface to surface distance is
at least 10 applies for any defect (vacancy, interstitial, stacking fault)

Do k-point convergence test

Since in one direction there is a vacuum and it is longer than other translational
lattice vectors set revelent k-point to 1
For the other 2 directions start off with values used for bulk calculation and do
convergence

Finally keeping the k-points and all other parameters fixed change
no. of bulk and vacuum layers

Look for convergence of surface energy

Remember to divide by 2 since periodic boundary conditions give rise
to 2 surfaces

Most common mistakes

Considering energy difference from calculations
that has different energy-cutoffs
If ENCUT is not specified default is largest ENMAX of
POTCAR
If adsorption energy is considered
E.g. adsorption of O atom on Al (111), Al ENMAX = 240 eV
while Co ENMAX = 400 eV

Considering energy difference from calculations

with two different k-point grids
Please read

http://cms.mpi.univie.ac.at/vasp/vasp/most_important
_parameters_source_errors.html

How to validate results

Increase cutoff

Recommended to set ENCUT by

hand
Change to PREC=Accurate

Increase no. of k-points

Increase slab thickness for
surface energy and adsorption
energy calculations
Increase the size of the
supercell for defects
To remove interaction of defect
with defect due to periodic
boundary condition

Homework 1
Each group will use different XC functional
LDA, GGA-PW 91 and GGA-PBE

DFT calculations

Energy-volume curves
Elastic constants
Vacancy formation energy
Interstitial formation energy (Both octahedral and tetrahedral)
Surface formation energy for (111), (110) and (001) surfaces
Extrinsic and intrinsic stacking fault energies
Plot generalized stacking fault curve

Lattice constant, bulk modulus, elastic constants

Defect energies vacancy formation and interstitial
Stacking fault energies Intrinsic and extrinsic
Surface formation energies
E-V plot and GSF plot

List of properties of Aluminum going up to atomistic scale

Divide calculations within group

Report on ICME website what/how you did calculations assigned to you.

Explain whether you got a well-converged result
You will submit a report and do evaluations of your group members

Visulization tools
VESTA

http://jp-minerals.org/vesta/en/
Windows, Mac and Linux

VMD

http://www.ks.uiuc.edu/Research/vmd/
Windows, Mac and Linux

OVITO

www.ovito.org/
Windows and Linux

XCrysDen

www.xcrysden.org/
Mac and Linux

References
VASP documentation
http://cms.mpi.univie.ac.at/vasp/vasp/

VASP workshop slides

http://cms.mpi.univie.ac.at/vaspworkshop/slides/documentation.htm

VASP tutorial @ ugent

http://users.ugent.be/~devpouck/dlstuff/VAPS_tutorial
11_01_2010.pdf