First principles study of

anion doped perovskites

related SrMnO3

Abdallah Abdelrahman M.
Ph.D. student
 Outline
 What are the first principles calculation?
 How an ab initio calculation works
 Hartree –fock approximation
 density functional theory
 What are perovskite
 Ab initio modeling in solid state physics
(CRYSTAL code)
 Result and discussion
What are the first principles
calculation?
 The world around us is made of condensed matter.

 The prediction of the behaviour of systems )

empirical or semi-empirical models)

Due to the complexity of condensed matter systems,

and the difficulty in building accurate models, the
predictive power of such an approach can be
severely limited.
the first principles
(ab initio) calculation are

 A method of calculating atomic and molecular

structure directly from the first principles of
quantum mechanics, without using quantities
derived from experiment (such as ionization
energies found by spectroscopy) as parameters.
How an ab initio calculation
works
 Ab-initio calculations require a large
amount of numerical computation.
 the amount of computing time required
increases rapidly as the size of the
atom or molecule increases.
 The development of computing power
has enabled the properties of both
small and large systems to be
calculated accurately, so that this form
of calculation can now replace semi-
empirical calculations.
Computational Methodology ab
initio electronic structure
methods
The Schrödinger equation for many
electrons

ˆ   R ; r    E   R ; r  
H I i I i

H is containing kinetic energy, external

potential and electron-electron coulomb
interactions +kinetic energy and ions-
ions interaction.
 2 2 ZIe2 1 e2
Hˆ     ri    
i 2m e i ,I ri  R I 2 i  j ri  r j
2 1 ZI ZJ e2
 I 
2

I 2M I 2 I J R I  RJ
Can be
ignored

And H can be written as

 2
ZIe2 1 e2 1 ZI ZJ e2
Hˆ     2ri      
i 2m e i,I ri  RI 2 i  j ri  r j 2 I  J R I  RJ

T̂
Vex t
Vint I-I
int
 The Hartree Approximation
 For a legal wavefunction (antisymmetric,
normalised)

H   ri    1  r1   2  r2 ....... N  rN 
 - the total energy is
Hˆ H

E H  H

  2  2r e2 1
 i  Vext  r   i    i j  i j
i 2m e 2 ji r  r
 - and the single particle Hartree

   2  2r 1 
  Vext  r   e   j
2
 j   i  r    i i  r 
 2m e j i r  r 
Hartree Fock Theory

An on set for the structure of wavefunction

1
HF   ri    det 1  r1   2  r2 ....... N  rN  
N!
   2  2r 1 
  Vext  r   e   j
2
 j  i  r 
 2m e j i r  r 
1
e   j
2
 i  j  r    i i  r 
j i r  r

Exchange
Term (V ex)
The Hartree Fock Equations
   2  2r  j  r  2  i  r , r 
ex 
  V ext  r   e 2  d r  e  d r    i  r    i i  r 
 2 m e ji r  r r  r 

 j r    j  r  2
 r    j r
j

 i  r    i  r    r   j  r 
 ex
 r , r   
j

 i  r   i  r 
i
j i

Non-interacting electrons under

the influence of mean field
potential consisting of classical
coulomb potential and non-local
exchange potential
Density functional theory
DFT – the theorems
 DFT theory is a theoretical
framework for treading the
complicated interactions in an N-
electron system leading to effective
one-electron equations.
 To find the exact ground state
energy knowledge of the charge
density ρ(r) is enough !
What are perovskites

CaTiO3

The perovskite unit cell ABX 3 where the larger A cation is

depicted in green, the B cations are shown in white and
the X anions are shown in red.
An expanded view of the
perovskite structure
Perovskite Structure:AMO3
 All Ions (M,O) Topologically
Equivalent Network of corner-
sharing MO6 octahedra
 2 cationic sites: different partition
of charge possible
 LaMnO3 (3-3)
 BaTiO3 (2-4)
 KNbO3 (1-5)
Ab initio Modeling in Solid State
Physics with
CRYSTAL Code

 The CRYSTAL package consists of two executables:

 • crystal
 performs integrals calculation and SCF part
 computes total energy and wavefunction
 performs geometry optimization
 calculates vibrational frequencies at G point
 • properties
 performs the wavefunction analysis (e.g. one-
electron properties)
CRYSTAL input scheme
 CRYSTAL input is given by keywords It
consists of three sections:
 0. Title
 1. Geometry input section
 2. Basis set input section
 3. Method & SCF input section
Ab initio Modeling of Hexagonal
Perovskite SrMnO3
1-Title
 SrMnO3 antiferromagnetic ud 1x1x2 194
 CRYSTAL 2-Dimensionality of the
 000 system
 194
 5.4434 9.0704 90 120 3- Crystallographic
 5 information (3D only)
 238 0 0 0
 238 0.333333 0.666667 0.25 4-Space Group (p63/mmc-
 25 0.333333 0.666667 0.6122 194)
 8 0.5 0. 0.
 8 -0.1807 -0.3614 0.25 5-Lattice parameters
 NOSHIFT (hexago.)
 SUPERCELL
 100 6-Number of non equivalent
 010 atoms Atomic number and
 002 fractional coordinates
 OPTGEOM
 FULLOPTG 7- optional keyword
 END
End of geometry input
 END
section
 Basis set input section
 84
 0 0 8 2.0 1.0 1-Atomic number and
 8020.0 0.00108
 1338.0 0.00804 number of shells
 255.4 0.05324 2-Basis set input:
 69.22 0.1681
 23.90 0.3581 2.1- code,
 9.264 0.3855
 3.851 0.1468 2.2-type, nr. of primitive,
 1.212 0.728
 0 1 4 6.0 1.0 2. 3-formal charge and
 49.43 -0.00883 0.00958
 10.47 -0.0915 0.0696 2.4-scale factor of the
 3.235 -0.0402 0.2065 shell.
 1.217 0.379 0.347
 0 1 1 0.0 1.0
 0.4764 1.0 1.0
 0 1 1 0.0 1.0
 0.1802 1.0 1.0
 99 0
CRYSTAL input – DFT input
block
1-DFT input block
 DFT
 SPIN 2- the system is spin-polarized
 B3LYP systems
 END
 SHRINK 3-correlation and exchange
 66
 SCFDIR
functional
 MAXCYCLE
 120
End of the DFT input block
 SPINLOCK
4-Reciprocal space integration
 0 120
 LEVSHIFT parameters
 61
 FMIXING 5- convergence utility
 30
 ATOMSPIN End of the Method input section
 8
 9 1 10 -1 11 1 12 -1 13 1 14 -1 15 1 16 -1
 PPAN
 END
CRYSTAL output
 EEEEEEEEEE STARTING DATE 18 07 2010 TIME 10:33:14.9
 SrMnO3 194 antferromagnetic ud

 CRYSTAL CALCULATION
 (INPUT ACCORDING TO THE INTERNATIONAL TABLES FOR X-RAY
CRYSTALLOGRAPHY)
 CRYSTAL FAMILY : HEXAGONAL
 CRYSTAL CLASS (GROTH - 1921) : DIHEXAGONAL DIPYRAMIDAL

 SPACE GROUP (CENTROSYMMETRIC) : P 63/M M C

 LATTICE PARAMETERS (ANGSTROMS AND DEGREES) - CONVENTIONAL CELL

 A B C ALPHA BETA GAMMA
 5.44340 5.44340 9.07040 90.00000 90.00000 120.00000

 NUMBER OF IRREDUCIBLE ATOMS IN THE CONVENTIONAL CELL: 5

 INPUT COORDINATES

 ATOM AT. N. COORDINATES

 1 238 0.000000000000E+00 0.000000000000E+00 0.000000000000E+00
 2 238 3.333330000000E-01 6.666670000000E-01 2.500000000000E-01
 3 225 3.333330000000E-01 6.666670000000E-01 6.122000000000E-01
 4 8 5.000000000000E-01 0.000000000000E+00 0.000000000000E+00
 5 8 -1.807000000000E-01 -3.614000000000E-01 2.500000000000E-01
 TTTTTTTTTTTTTTTTTTTTTTTTTTTTTT MOQGAD TELAPSE 6567.71
TCPU 6555.49
 TTTTTTTTTTTTTTTTTTTTTTTTTTTTTT SHELLX TELAPSE 6650.92
TCPU 6638.60
 +++ ENERGIES IN A.U. +++
 ::: EXT EL-POLE -3.8645620245026E+03
 ::: EXT EL-SPHEROPOLE 4.5938172844779E+01
 ::: BIELET ZONE E-E 4.1965071955803E+03
 ::: TOTAL E-E 3.7788334392249E+02
 ::: TOTAL E-N + N-E -2.1603424670753E+03
 ::: TOTAL N-N -5.9233952856580E+02
 ::: KINETIC ENERGY 1.0698788970100E+03
 ::: PSEUDO TOTAL ENERGY -1.3049197547086E+03
 ::: VIRIAL COEFFICIENT 9.0102703758549E-01
 TTTTTTTTTTTTTTTTTTTTTTTTTTTTTT MONMO3 TELAPSE 6655.50
TCPU 6643.18
 NUMERICALLY INTEGRATED DENSITY 98.0349663745 98.0346135635
 TTTTTTTTTTTTTTTTTTTTTTTTTTTTTT NUMDFT TELAPSE 6670.33
TCPU 6657.99
 CYC 42 ETOT(AU) -1.437717843287E+03 DETOT -6.06E-08
tst 9.51E-09 PX 4.22E-05

 == SCF ENDED - CONVERGENCE ON ENERGY E(AU)

-1.4377178432867E+03 CYCLES 42
 GRADIENT NORM 0.000867 GRADIENT
THRESHOLD 0.500000

 PREDICTED ENERGY CHANGE -0.459E-06

 MAX GRADIENT 0.000445 THRESHOLD

0.000450 CONVERGED YES
 RMS GRADIENT 0.000210 THRESHOLD
0.000300 CONVERGED YES
 MAX DISPLAC. 0.001365 THRESHOLD
0.001800 CONVERGED YES
 RMS DISPLAC. 0.000413 THRESHOLD
0.001200 CONVERGED YES

 CONVERGENCE TESTS SATISFIED AFTER 17

ENERGY AND GRADIENT CALCULATIONS

 ******************************************************************
 * OPT END - CONVERGED * E(AU):
-1.437719141045E+03 POINTS 17 *
 ******************************************************************
OVERLAP POPULATION
CONDENSED TO ATOMS FOR
FIRST 6 NEIGHBORS
 4 SR ( 0 0 0) 6.352 3.361 0.000
 ATOM A 9 O ATOM B CELL R(AB)/AU R(AB)/ANG
OVPOP(AB)
 8 MN ( 1 0 0) 3.555 1.881 0.023
 6 MN ( 1 1 0) 3.555 1.881 0.023
 11 O ( 0 -1 0) 5.130 2.715 -0.001
 1 SR ( 0 0 0) 5.130 2.715 0.000
 11 O ( 1 0 0) 5.130 2.715 -0.001
 17 O ( 0 0 0) 5.153 2.727 -0.001
Results and discussion
Structure of hexagonal
SrMnO3
THANK FOR YOUR ATTENTION