Attique ur Rehman

DFT Calculation of Single

(NE03)
Supervisor : Dr.

Crystal Radiation Detector

Muhammad Sohail
Co- Supervisor: Dr.
Mujtaba ul Hassan
Projective Objectives

• Systematic theoretical calculations based on the density

functional theory method will be performed on scintillation and
semiconductor radiation detector crystals.
• The calculation for obtaining band structure, density of state as
well as optical properties using DFT codes such as Wein 2k and
ELK.
Project Motivation
• To better Understand
• Ground State Energies, Density of States and the Band Gap
• Electric, Magnetic and optical Properties
• Electronic structure
• Behavior of semiconductor Radiation detectors under
different fields.
• Predict crystal structure
• A better detector can be build based of better understanding
these properties
What Is DFT
• Density Functional Theory as a way to solve the quantum many body
problem.

• The Basics of all Quantum Mechanical Calculations of electronic

structure of material is Schrodinger Equation

 2
 2Ri
 2
 r2i
1 e2 1 e2 1 e2 Zi Z j
H 
2

i

Mi 2
i m  4 
i, j
  
Ri  rj 8  i  j ri  rj 8 
 R R
i j
e  i j

Hˆ tot  TˆN  Tˆe  Vˆee  VˆNN  VˆeN

Approximations

• The Born-Oppenheimer approximation

• The nuclei are much heavier and therefore much slower than the
electrons hence ‘freeze’ them at fixed positions.
• First term disappears. The last term reduces to a constant.
Hˆ tot  Tˆe  Vˆee  Vˆext
• The Hartree Fock Theory
• Thomas Fermi Model
The theorems of Hohenberg and Kohn

• First theorem:
There is a one-to-one correspondence between the ground-state density
ρ(⃗r) of a many-electron system (atom, molecule, solid) and the external
potential Vext.
<Ψ| Oˆ| Ψ> = O[ρ]
• Second theorem:
The electron density that minimizes the energy of the overall functional is
the true electron density corresponding to the full solution of the Schrödinger
equation.
KOHN-SHAM METHOD
One initially guesses at a set of wave functions ψi0, from
which is constructed an initial electron density ρo
N
 (r )    i (r )
2

i 1
 (r1 )
vKS (r )  vext (r )   dr1  vxc (r )
r  r1
1 2
H ks     vKS (r )
2
H ks  i (r )   i  i (r )
THE EXCHANGE-CORRELATION FUNCTIONAL

• The LDA
This approximation uses only the local density to define the
approximate exchange–correlation functional, so it is called the local
density approximation (LDA).
• The GGA
The best-known class of functional after the LDA uses information
about the local electron density and the local gradient in the electron
density; this approach defines a generalized gradient approximation
(GGA).
ELK EXERCISES and Reproduction of David S. Sholl’s
Results for Cu

• Crystal structure preparation

• Ground state energy calculation
• Density of States
• Charge density and electron localization function
• Optimization of Lattice parameters
Crystal structure preparation
• For the crystal structure preparation the program spacegroup is used.

MgB Crystal Structure prepared by

XCrysDen from the Crystal file
prepared by Space Group Utility
Ground state energy calculation
• Ground state energy is calculated woth Tast 0 and 1
• The Ground State Energy is calculated in Hartree .
• 1 Ha = 27.21138505 eV

• The total energy for the gray Sn (-12358.1766339 Ha for 2

atoms in the primitive cell) is lower than for the white Sn (-12358.1743978 Ha
for 2 atoms in the primitive cell) and is more energetically advantageous
structure at low temperatures.
• Similarly ground Stare energy for Ge, Cu, Pb were also calculated.
Density of states of Ge and Pb
Partial Density of States
Density of states of Ge and Pb
Density of states of Ge and Pb
 Charge density and electron localization
function of Si

The Charge Density of Silicon is more near the lattice site and then decreases
exponentially until the center of the bond and then again increases
exponentially until lattice site.
 Reproduction of David S. Sholl’s Results
for Cu
• Total energy, E, of Cu in the FCC Crystal Structure as a Function of the Lattice Parameter, a.
• The calculations are made using fcc Cu with 4 Cu atoms, Cut off energy of 200eV and 12*12*12 k-
points.
• With GGA as defined by Perdew-Wang 91 method.
Energy/atom
-1655.415
3.3 3.4 3.5 3.6 3.7 3.8 3.9 4 4.1

-1655.42

f(x) = 0.126811390191626 x² − 0.929668138537057 x − 1653.73172949941

-1655.425
E/atom (Hatree)

-1655.43

-1655.435

-1655.44
a (Angstrum)
 Total energy, E, of Cu in the Simple Cubic Crystal Structure as a
Function of Lattice parameter, a.

Simple Cubic
-1655.36
2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3
-1655.37

-1655.38
E/Atom Hartree

f(x) = 0.120803521644218 x² − 0.589813892549715 x − 1654.70119990824

-1655.39

-1655.4

-1655.41

-1655.42

-1655.43
a(A)

The minimum energy we get is at 2.4 Angstrom which is -1655.425 Ha. This energy is
greater than fcc i.e -1655.463Ha So Cu is Fcc
 Variation of Energy With k-points

no of k
points -1655.32
0 2 4 6 8 10 12 14 16
k E E/atom in IBZ time
1 -6621.458495 -1655.364624 1 16.22 -1655.34
2 -6621.710963 -1655.427741 4 24.18
3 -6621.726263 -1655.431566 4 29.64
-1655.36
4 -6621.743252 -1655.435813 10 43.44
5 -6621.738916 -1655.434729 10 44.68
6 -6621.742999 -1655.43575 20 81.69 E/atom (Hatree -1655.38

7 -6621.744328 -1655.436082 20 78.81

8 -6621.743873 -1655.435968 35 131.97 -1655.4 f(x) = 0.00067740184064706 x² − 0.0125097719338456 x − 1655.38518172126
9 -6621.744404 -1655.436101 35 144.98
10 -6621.744062 -1655.436016 56 234.03 -1655.42
11 -6621.743987 -1655.435997 56 222.05
12 -6621.744172 -1655.436043 84 368.6
-1655.44
13 -6621.74409 -1655.436023 84 380.11
14 -6621.744225 -1655.436056 120 535.73 k values
-1655.46
 Trend of Energy with Energy Cut-off
Values.

Energy Cut off

-1655.4406
100 120 140 160 180 200 220 240 260 280

-1655.4408

-1655.441
E/Atom (Hartree)

f(x) = 1.38467410770972E-07 x² − 6.54096125252331E-05 x − 1655.4341552695

-1655.4412

-1655.4414

-1655.4416

-1655.4418

-1655.442
E cut off (eV)
Summery and Conclusion
• These were the few tasks that were performed until know to understand
how the program works and how we can perform our required
calculations.
• Most Important of which is the Ground State Energy Calculation and The
Density of States.
• These tasks are Benched marked with the available literature and found
Correct.
Future Work
• Further Study the theoretical background.
• Application of DFT on Ge and other semiconductor crystals detectors.
THANKS ANY QUESTIONS?