Potential energy profile of

benzene adsorption on surface

layer of SrTiO3: DFT
calculation
FINAL YEAR PROJECT 2
Name Matric Course Code
NOH KHAIRIL FITRI BIN
191032900 RK86
KHAIRUDDIN
AGENDA
• INTRODUCTION

• PROBLEM STATEMENT

• OBJECTIVES

• LITERATURE REVIEW

• METHODOLOGY

• RESULTS AND DISCUSSION

• CONCLUSION
 Chapter 1 | Introduction
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What is Strontium titanate (SrTiO3)?

● A perovskite-type oxide whose physical characteristics are strongly
influenced by its chemical composition, structure, shape, size, and
crystallinity goals

What is Benzene (C6H6)?

● An organic chemical compound with its characteristics being a
colorless/yellowish liquid, smell sweet and highly flammable
● Used as mediator for electron transferring
 Chapter 1 | Introduction

What is Adsorption?
● The adhesion in an extremely thin layer of molecules (as of gases, solutes,
or liquids) to the surfaces of solid bodies or liquids with which they are in
contact compare absorption
● This project intends to find the potential energy profile of SrTiO3 when
benzene is adsorbed on its surface

Exp of adsorption of Benzene on

Hematite (α-Fe2O3) Surfaces
 Chapter 1 | Introduction

PROBLEM STATEMENT
● No quantitative experimental determination of the adsorption behavior of
benzene on SrTiO3.

● Too few reports on the study of SrTiO3’s electronic and optical properties and
its potential as a catalyst for benzene reactions.
 Chapter 1 | Objectives Chapter 1 | Project Scope

● To examine the electronic

● Using Quantum Espresso/BURAI
characteristics, DOS band diagram
software for DFT based calculations
(band diagram), and simple cubic ● Using VESTA software for 3D
and hexagonal 3D polymorphs of
visualization and modelling benzene
SrTiO3
adsorption on SrTiO3
● To analyze the potential energy
profile of benzene on the SrTiO3
surface.
● To determine how benzene
adsorption affects the electronic
structure of the SrTiO3 surface.
 Chapter 2 | Literature Review
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Density functional theory

● Method to calculate physical properties directly from
basic physical quantities such as the mass and charge,
Coulomb force of an electron based on the principle of
quantum mechanics

Kohn-sham equations
● A more detailed version of DFT​, explains the correlations
of electron densities to their molecular energies
● Kohn-Sham solve electron density of the reference
system (structure that needs to be calculated) to be the
same as that of the real system
 Chapter 2 | Literature Review
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Generalized Gradient Approximation

● The generalized gradient approximation (GGA) has been
a workhorse exchange–correlation functional for
electronic structure studies of extended systems

Overview of GGA calculations

● Could describes bonding descriptions more accurately
● Could underestimate the band gaps by 30 percent
● Use reasonable computational costs

exchange–correlation functional
 Chapter 3 | Methodology

PROJECT
FLOWCHART
 Chapter 3 | Methodology

Computational Calculations

• The surface calculations are based on the

SrTiO3 structural model obtained from
the MaterialsProject website

• Model was built as a slab with vacuum

space gaps between the lattice, with the
intention of simulating the interphase over
a solid system's surface
 Chapter 3 | Methodology

Self-Consistent Field

• The main goal is to find the atomic

configuration with the lowest energy

• Electronic density is calculated repeatedly

to enhance the description until there is
little to no change in the outcomes, or
until the electronic density is "self-
consistent“
 Chapter 3 | Methodology

Density-of-States

• The number of various states that

electrons are permitted to occupy at a
specific energy level, or the number of
electron states per unit volume per unit
energy

• Allow one to calculate the general

distribution of states as a function of
energy

• Specifies how many states the system will

occupy at each level of energy
 Chapter 3 | Methodology

Band Structure

• Explains the range of energies that an

electron within a material can or cannot
have

• The band structure can be utilized to find

the bands that cross the Fermi level

• A band structure calculates the direct and

indirect band gap in characterizing the
electrical conductivity of the solid
 Chapter 4 | Results and Discussion

• Adsorbed benzene has a parallel

orientation with respect to SrTiO3.

• Varying distance between benzene and

SrTiO3 surface explained.

• No direct chemical bonds between

benzene and oxide substrate atoms. Geometry A Geometry B Geometry C

• Stability of adsorbed benzene is Parameters Geometry

measured and calculated A B C

• Geometry B has Benzene ring

Distance from No benzene 1.5 Å 3Å
symmetrical around surface Sr atom, C- Srtio3
Sr distance of 1.5 A while Geometry C
adds another 1.5 A to the distance
 Chapter 4 | Results and Discussion

SCF Convergence

• All three simulated geometries were analyzed for convergence assessment.

• Quantum Espresso scripting starts with an "SCF" calculation type for &CONTROL
scripting.

• Force threshold set at 0.00038 Ry/bohr for convergence.

• Gaussian broadening of 0.002 Ry used to smooth DOS peaks and enhance convergence.

• Wavefunction Cutoff Energy/ecutwfc set at 30 Ry.

Element Filename P.P

• Charge Density Cutoff Energy/ecutrho set at 180 Ry.
Sr Sr_pbe_v1.uspp.F.UPF USPP
• Occupancy set to smearing.
Ti ti_pbe_v1.4.uspp.F.UPF USPP
• Convergence threshold (Ry) set at 0.01 for determining level of convergence. O O.pbe-n-kjpaw_psl.0.1.UPF PAW

• Maximum iteration steps set at 100 steps. C C.pbe-n-kjpaw_psl.1.0.0.UPF PAW

H H_ONCV_PBE-1.0.oncvpsp.upf NC
 Chapter 4 | Results and Discussion

SCF Convergence

Geometry Number of SCF Final energy/Ry

iterations
A 8 Converged -5036.51774
B 8 Converged -5153.67457
C 8 Converged -5154.11668
• B and C have a decreased on final energy of 117 Ry and 118 Ry respectively
 Chapter 4 | Results and Discussion

SCF Convergence

NO OF Total Energy
ITERATIONS A B C

1 -5027.381 -5145.292 -5145.551

2 -5017.365 -5139.005 -5139.656
3 -5036.489 -5153.396 -5153.892
4 -5036.662 -5153.770 -5154.216
5 -5036.412 -5153.581 -5153.955
6 -5036.512 -5153.656 -5154.111
7 -5036.52 -5153.667 -5154.102
8 -5036.517 -5153.674 -5154.116
 Chapter 4 | Results and Discussion

SCF Convergence

• No significant difference between geometries B and C in terms of total energy.

• Convergence observed after the third iteration, indicating a self-consistent electronic

structure solution.

• Geometries with benzene adsorption (B and C) on SrTiO3 have lower total energy
than benzene-less material (A).

• Benzene adsorption indicates a more stable electronic configuration for SrTiO3.

• More stable SrTiO3 predicts more reliable behavior and characteristics, less prone
to sudden changes.
 Chapter 4 | Results and Discussion

Band Structure

Geometry A Geometry B Geometry C

Geometry Bandgap (eV) Fermi level (eV)

A 0.5036 0.2059
B 0.59140 0.4211
C 1.00310 0.4124
 Chapter 4 | Results and Discussion

Band Structure
• Geometry B have the most partially filled and overlapping energy bands

• Geometry C have a higher bandgap in comparison to B and A

• Geometry B and C shows that adsorption of benzene widens the bandgap of SrTiO3,
which when manipulated properly to can be used to efficiently absorb or emit
photons with higher energies, enabling their functionality in the ultraviolet or visible
regions of the electromagnetic spectrum.

• The adsorption also increases both the fermi level on Geometry B and C
 Chapter 4 | Results and Discussion

Band Structure

Geometry A Geometry B Geometry C

Geometry B
Geometry C
• Higher spread of states/broader
• Concentrated states in areas/higher
distribution.
peak.
• Exhibits higher electronic state
• Indicate the presence of energy levels
density, enhancing electronic mobility,
that are more favorable for electronic
optical absorption, and electronic
transitions.
transitions within the material.
 Chapter 4 | Results and Discussion

Charge Density

Geometry Charge Density(e/bohr³) Total Field Potential(e/bohr³)

ρ(max) ρ(min) ρ(max) ρ(min)

A 1.3798 -0.44889 0.37219 -17.303

B 1.5817 -0.44941 0.53117 -17.3270

C 1.5798 -0.44889 0.53601 -17.2790

 Chapter 4 | Results and Discussion

Charge Density

• Geometry B and C exhibit higher charge density and total field potential compared
to geometry A.

• Higher charge density implies a stronger electric field added to SrTiO3 by the
adsorption of benzene.

• The higher values in Geometry B and C suggest improved electron flow and
potentially enhanced performance.

• Higher charge density can lead to increased absorption of light due to a higher
number of available electronic states for electronic transitions.
 Chapter 4 | Results and Discussion

Charge Density

Geometry A Geometry C

Geometry B
 Chapter 4 | Results and Discussion

Charge Density / Total Field Potential

Geometry A Geometry C

Geometry B
 Chapter 5 | Conclusion
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Conclusion
● Based on the SCF calculations, benzene adsorption could add improve the accuracy in
getting stable SrTiO3 electronic and optical properties
● Benzene adsorption has been shown to induce significant changes in the material's
properties, including modifications in the band structure, and the charge density
● The improved electronic and optical properties on SrTiO3 with benzene adsorption could
contribute further developments on solar and optoelectronics.
 Chapter 5 | Conclusion
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Future Work
● Future studies on benzene adsorption on SrTiO3 can enhance our understanding of interactions
between organic molecules and perovskite materials.
● Research can focus on uncovering the fundamental mechanisms and dynamics of benzene
adsorption, including the role of surface defects, crystallographic orientations, and surface
terminations.
● Advanced computational techniques, particularly density functional theory (DFT)
computations, such as various meta-GGA+U approaches, can provide more precise simulations
and predictions of benzene adsorption behavior and energetics.
Editable Icons
 Norm-Conserving pseudopotentials focus on accurate reproduction of valence electrons, Ultrasoft pseudopotentials provide computational
efficiency with reduced basis sets, and PAW pseudopotentials combine accuracy and transferability by explicitly treating both valence and core
electrons.