Theoretical Insights into the Stability and Electronic Structure of

PtSeTe monolayer

Project Report

Submitted in Partial fulfilment of the requirement for The Degree of the

Master of Science (Sem-2)

By

PATEL ABHAY MAHESHBHAI

SHUKLA AKASH PARMATMASHARAN

Under the guidance of

Prof. (Dr.) P. N. Gajjar
Department of Physics,
University School of Sciences,
Gujarat University, Navrangpura,
Ahmedabad, 380009

2024 – 2025
pg. 2
 Certificate
This Project report submitted by Patel Abhay Maheshbhai (Seat No:01) & Akash P.

Shukla (Seat No: 37), entitled, “Theoretical Insights into the Stability and Electronic

Structure of PtSeTe monolayer” has been examined under the Guidance of Prof. (Dr.) P.

N. Gajjar. This report is accepted as fulfilling the partial requirement for the project and

for the degree of Master of Science in Physics during the academic year 2024-2025.

________________________ ________________________

Patel Abhay Shukla Akash

Professor In-charge Head of the Department

Prof. (Dr.) P. N. Gajjar Prof. (Dr.) R. B. Jotania

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pg. 4
 Declaration

It is to be declared that the project titled “Theoretical Insights into the Stability and
Electronic Structure of PtSeTe monolayer.”. Submitted for the degree of the Master of
Science (Sem-2) in Physics, is the record of research work carried out during the period from
1/03/2025 to 5/04/2025 under the guidance of Prof. (Dr.) P. N. Gajjar. We further declare that
the material obtained from other sources has been duly acknowledged in the project report. We
shall be solely responsible for any plagiarism or other irregularities, if noticed in the report.

Signature of the candidate Signature of the candidate

Patel Abhay (Roll no:01) Shukla Akash (Roll no:04)
[Link]. (Sem-2) Student [Link]. (Sem-2) Student
Department of physics Department of physics,
University School of Sciences University School of Sciences,
Gujarat University Gujarat University,
Ahmedabad – 380 009 Ahmedabad – 380 009

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pg. 6
 ACKNOWLEDGMENT

It is our pleasure to acknowledge and express convivial thanks to our guide, colleagues, and all
the person without whom this work would not have been accomplished.

First, we would like to express our heartfelt gratitude to our guide Prof. (Dr.) P. N. Gajjar for
his continuous support and guidance at every stage. We would like to thank to entire members
of the Department of Physics, Gujarat University who have assisted us in our studies and
provided us departmental facilities and their encouragement have been able us to complete
successfully this project.

We would also like to express sincere thanks to our senior and Ph.D. Scholars Mr. Utsav
Prajapati, Mr. Nikhil Solanki, Mr. Bhargav Darji, Ms. Niyati Gajjar and Mr. Suresh
Chaudhari who helped us during this project.

Finally, we would like to express our gratitude towards those who helped us directly and
indirectly during project.

Signature of the candidate Signature of the candidate

Patel Abhay (Roll no:01) Shukla Akash (Roll no:04)

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pg. 8
 Index

1. Introduction
a. Objection
2. Methodology
3. Results and Discussion
a. Structural Configuration
b. Phonon Dispersion Curves
c. Cohesive Energy
d. Electronic Properties
4. Conclusion
5. Reference

pg. 9
pg. 10
 Introduction
A driving force behind the development of revolutionary technologies has been
materials science, enabling the detailed study of material properties, including electronic and
chemical properties, as well as phonons. This study has provided the foundation for
understanding electron propagation in crystals through quantum mechanics, and for
differentiating between metals, semimetals, semiconductors, and insulators. This progression
has been significantly influenced by the vision articulated by Richard Feynman in his seminal
1959 lecture, "There' is Plenty of Room at the Bottom."[1] Feynman's prescient words sparked
a revolution, igniting the field of nanotechnology and foreshadowing the incredible potential
of manipulating matter at the atomic and nanometre scales.

Feynman's lecture served as a catalyst, propelling materials science towards

unprecedented precision and control. It challenged scientists to think beyond conventional
approaches and delve into the realm of the extremely small, paving the way for the development
of techniques to fabricate and characterize materials with atomic precision. This pursuit led to
significant advancements in our understanding of fundamental material properties, including
electronic, chemical, and phononic behavior, ultimately providing a deeper insight into electron
propagation within crystalline structures through the lens of quantum mechanics. Furthermore,
this period witnessed a refined understanding of the distinctions between metals, semimetals,
semiconductors, and insulators.

Following this impetus, significant attention has been devoted to the investigation of
material properties of atomic systems within condensed matter physics. The Schrödinger
equation, a mathematical formalism of quantum mechanics, has allowed for solving the many-
electron Schrödinger equations by self-consistent methods, yielding solutions for many-body
problems at the atomic scale. From a theoretical perspective, this facilitates the exploration of
the physical descriptions of multi-electron atoms. To probe and design material properties,
including electronic, magnetic, optical, superconducting, physical, structural, chemical, and
thermal properties of condensed matter atomic systems, a range of experimental and theoretical
methods are available, notably first-principles methods such as density functional theory
(DFT), a quantum mechanical model.

Due to the increase in attraction with two-dimensional (2D) substances, driven by the
finding of graphene, there is possibility of stable sp2-bonded phase of materials other than
carbon has attracted much scientific interest. The unique qualities of 2D materials, such as their

pg. 11
reduced dimensionality and symmetry, lead to the appearance of phenomena that are very
different from those of their bulk material counterparts. A graphene-like structure can also be
formed by combining boron and nitrogen, which, like carbon, belong to the first row of the
Periodic Table. The resulting sp2-bonded single-layer hexagonal boron nitride (BN) structure
is a wide-band-gap semiconductor with a gap of 5.8 eV [2]. Furthermore, the combinations of
C, B, and N have also been used to propose hybrids of graphene and BN. The restrictive nature
of the optimization performed for these structures, however, does not allow one to affirm their
stability with any certainty.

Following the exploration of materials like hexagonal boron nitride, a new class of 2D
materials gained prominence. The major milestone in journey of nanoscience came with
discovery on new class of material i.e. Janus material. The material has two faced structure
like roman god Janus. Similar two-faced structure can be observed in leaves of lotus plant (top
side is hydrophobic and back side is hydrophilic). In 2009, Bekyarova et al [3] reported a
material that is asymmetrical. This asymmetricity can be utilized for analysis of properties and
functionalities. These material has wide application in field of photocatalysis. Janus materials,
characterized by their distinct top and bottom surfaces. In this work we propose a new lattice
with bonding configuration consisting of Pt, Se, and Te.

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 Objectives
The main objectives of the project entitled “Investigation of structural stability and
electronic properties of PtSeTe monolayer using DFT approach” are as follows:

• To study the structural properties of PtSeTe monolayer (ML) using density functional
theory (DFT).
• To assess the structural stability of the PtSeTe monolayer, we have investigated its
thermodynamic and dynamical stability.
• Thermodynamic stability is evaluated through cohesive energy, dynamical stability is
examined using phonon dispersion curves.
• To study electronic band structure of Janus PtSeTe ML.
• To investigate total density of states (TDOS) and partial density of states (PDOS) of
Janus PtSeTe.

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pg. 14
 Methodology
Research on material properties has become more active since there are many
approaches to investigate various material properties in which presently, a new approach
density functional theory (DFT) has achieved more and more fame since last decade, which
involves innovation of material structure to analysis of material properties.

DFT is a fast, efficient, and widely used computational technique in different branches
of science especially physics, chemistry, computational material sciences and geophysics to
achieve desired solutions of complex condensed matter system. Moreover, DFT has broad
application in the chemical and material science for the interpretation and prediction of
complex behaviour of material at an atomic scale based on their properties obtained from
computations.

Initially, DFT has roots in 1926 in the theoretical approximation of Thomas and Fermi
was developed to deal with only ground-state properties, later it gains better in sight as almost
after 40 years. In 1964, the initial work on DFT was reported in the published paper entitled
“Inhomogeneous electron gas” by Hohenberg and Kohn that the ground state energy of this gas
can be described entirely by a functional of electron density.

Depending on this work, Kohn and Sham have demonstrated many body problems can
be substituted by a self-consistent equation like Hartree and Hartree-Fock. This self-consistent
method is useful approach to investigate various material properties such as electronic,
magnetic, physical, optical, thermal, structural, chemical, vibrational, superconducting
properties, etc of many bodies atomic system. DFT includes various codes, which have been
developed to precisely compute the material properties where the focus is electron density ρ(r),
a physical property of the material that is easily measurable. As DFT requires only the inputs
of crystallographic information, i.e. parameter free therefore it is called first principles theory.
The tremendous growth in computing power have engrossed the researchers to implement DFT
with various codes as it consumes less time in investing material properties of complex systems
compared to other quantum theoretical investigations based on wave functions [6].

There is various implementation codes based on DFT like Ab-initio, Quantum

ESPRESSO (Quantum open-source package for research in electronic structure, simulation,
and optimization), VASP (Vienna ab‐initio simulation package), CASTEP (Cambridge serial
total energy package), SIESTA (Spanish initiative for electronic simulations with thousands of
atoms), Wien2k etc. These DFT based codes differ from each other by the capability of

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computation of material properties and the implementation method, which are used in that
codes to investigate the properties. Hence, it provides complementary perspectives.

• Exchange and correlation functional

It contains the corrections to the Kohn-Sham one body effective potential, as well as the
effects of the correlations between identical particles. Model functional can then be produced
which satisfy as many of those constraints as possible. This model can be tested against simple
systems like the uniform electron gas, or systems that are somewhat more complicated. In this
way, different functional have been derived for systems ranging from single atoms to complex
materials.

Functional Uxc[n] are generally divided into two classes, namely the local density
approximation (LDA) and the generalized gradient approximation (GGA).

GGA has overcome on LDA by solving one deficiency of the LDA. The exchange and
correlation function GGA is similar to LDA. The only difference in GGA, is the exchange
energy is dependent on both the local density as well as the gradient of that electron density.
Exc[n(r)]=⎰f[n(r),∇n(r)]dr where, the function f is chosen by some set of criteria.

Here, the study uses Troullier-Martins type PBE (Perdew, Burke and Ernzerhof)
pseudopotential within the framework of GGA [5]. But the results of many applications as well
as formal analysis suggest that GGA functional are still too limited to yield a fully consistent
improvement over the LDA. The self-consistent way to solve Kohn-Sham equations is
described below by flow chart.

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 Figure 1. show a chart of self-consistent method

• Software and Tools

To optimize and visualize the crystal structure and study electronic properties of PtSeTe
in the present study computational tools SIESTA, Xcrysden, GDIS and XMgrace have been
used.

• SIESTA Code

SIESTA (Spanish initiative for electronic simulations with thousands of atoms) is an

original method and its corresponding computer program implementation, to perform efficient
electronic structure calculation and ab-initio molecular dynamics simulations of different
molecules and solids [4]. It utilizes the standard Kohn-Sham self-consistent density functional
method in local density (LDA-LSD) and the generalized gradient approximations, and also in
local functional which include van der waals interactions.

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 It uses norm-conserving pseudopotential in their fully non-local form. It also uses
atomic orbitals as a basic set, allowing double-zeta and angular momentum, polarization. It
projects the electronic wave functions and density onto a real-space grid in order to calculate
the Hartree and Fock exchange-correlation potentials and their matrix elements. The use of
linear combination of numerical atomic orbitals makes SIESTA a flexible and efficient DFT
code, providing simulations with several hundred atoms. SIESTA is written in Fortran-95 and
memory is allocated dynamically. It can be compiled for serial execution and for the parallel
execution, under the message passing interface (MPI).

Since 13th May 2016, with the release of SIESTA-4.0, the package is distributed under
the terms of the GNU public license (GPL). The parallel of SIESTA is highly efficient and can
bring down the computational costs significantly, if used wisely. A wide variety of post-
processing tools for SIESTA have been developed that can be helpful to process the outputs
obtained or also to supplement the functionality of the program.

• GDIS

GDIS (GTK Display Interface for Structure) is a scientific visualization program for
the display, manipulation, and analysis of isolated molecules and periodic structure. It is a
‘GIMP(GNU Image Manipulation Program) tool kit’(GTK) based processing tool. A key
feature of the package is the mechanism for constructing and manipulating arbitrary crystal
surfaces. It is in development stage, but is still quite functional. It supports file types like CIF,
BIO-SYM, XYZ, XTL, GULP, MARVIN, FDF, etc. GDIS is powerful tools set for computing
surface and interfacial properties and predicting crystal morphologies and also included
modules for computing powder diffraction pattern, generating molecular surfaces, and
analyzing dynamics trajectories. Furthermore, the program may be used as graphical interface
to simplify the construction of input files for the command lines various code like SIESTA.
The source code is distributed under the GPL.

• XCrysden

XCrySDen, stands for ‘X-window Crystal Structure and Densities’ is mainly used for
crystalline and molecular structure visualization fir aiming to display of isosurfaces and
contours, which can be superimposed on crystalline structures and interactively rotated and
manipulated. XCrySDen can read molecular structure from. XSF (XCrySDen Structure File)
format.

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 It runs on GNU/UNIX platforms. It also simplifies some tools to analyse properties in
reciprocal space viz selection of k-paths in the Brillouin zone to plot the band structure along
the symmetry point of given structure and to visualize comparable Fermi surface. In present
work, XCrySDen consumed for structure visualization of materials.

• Computational Parameters Used for the Simulations

In the present study, the first principles calculations are based on density functional
theory (DFT) implemented in SIESTA code using the atomic orbitals basis set with double zeta
polarization (DZP). The electron-ions interaction was treated using norm-conserving
pseudopotential. The Exchange-correlation functional were treated with generalized gradient
approximation (GGA) formed by Perdew, Burke and Ernzerhof (PBE) [5]. The optimization of
PtSeTe was developed over a 12 × 1 × 12 Monkhorst-Pack for sampling of brillouin zone (BZ)
[7]. We choose energy cut-off 450 Ry, so that total energy was conserved to within 1.0
meV/atom. Using the conjugate gradient (CG) method until the force on each atom was lower
than 0.01eV/Å. To eliminate interactions between neighbouring layer, a vacuum of about 18
Å was applied in the z direction. The band structure was obtained along the Г-M-K-Г high
symmetry point.

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pg. 20
 Results and Discussion

a. Structural Properties of PtSeTe monolayer

The unit cell of PtSeTe monolayer shows in Figure 1. which consist of three atoms
namely Platinum (Pt), Selenium (Se) and Tellurium (Te). PtSeTe monolayer (ML) possesses a
planar honeycomb lattice, shown in Figure-2. The optimized lattice constant for the unit cell
of PtSeTe monolayer is a = b = 3.90 Å. The optimized bond length between Pt-Se is 2.61Å, Pt-
Te = 2.67 Å. While, the bond angles between Pt-Se-Te is 177.55º. PtSeTe is composed of three
atomic layers, where the Pt atom layer is positioned between the Se layer and the Te layer.

(a)

(b)

Figure 2. (a) Top and (b) side views of optimized structure of Janus PtSeTe ML.

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 b. Phonons dispersion curves
The phonon dispersion curve is a plot that shows the relationship between the frequency
and wave vector of phonon in a crystal. Phonons are quantized lattice vibration that propagate
through a crystal lattice, and their behaviour is governed by the crystal's structure and
properties.

A quantized crystal vibration or the quantum unit of a crystal vibration is called a

phonon. To compute the dynamical stability of the structure, vibration spectrum is studied
which is displayed in Figure 3. In Figure 3 in which lower modes considered as an acoustical
modes and rest of others are categorized as optical modes. All the phonons mode of monolayer
PtSeTe are positive, which suggests PtSeTe ML is dynamically stable.

Figure 2. Phonon dispersion curves

c. Cohesive Energy
Cohesive energy is the minimum amount of energy required to separate a solid into
individual atoms or molecules. It measures the strength of the forces holding atoms or
molecules together in a material. In solid-state physics, cohesive energy is crucial in
understanding the stability of materials. The negative cohesive energy indicates the higher
stability of the structure.

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The Equation of cohesive energy is given by,

𝑬𝑷𝒕𝑺𝒆𝒕𝒆 −[𝒏𝑬𝑷𝒕 +𝒏𝑬𝑺𝒆 +𝒏𝑬𝑻𝒆 ]

Ecoh =
𝑵

Where, 𝐸𝑃𝑡𝑆𝑒𝑇𝑒 is the total energy of PtSeTe. And EPt, ESe, ETe are energies of platinum, selenium
and tellurium atoms, respectively. N is the number of total atoms in unit cell. We get the value
of cohesive energy -3.37 eV/unit cell of the 2D PtSeTe monolayer. Negative value of cohesive
energy indicate that PtSeTe ML is thermodynamically stable.

d. Electronic Properties
The electronic band structure of a crystal refers to the distribution of energy levels
available to electrons within the crystal lattice. This structure plays a crucial role in determining
the electronic properties of materials and is an important concept in the study of solid-state
physics.

In a crystal, electrons occupy discrete energy levels called bands. These bands can be
thought of as energy zones, where the energy levels within each zone are closely spaced
together. The lowest energy band that is fully occupied by electrons is called the valence band,
while the next higher energy band, which is typically partially occupied by electrons, is called
the conduction band.

The energy gap between the valence and conduction bands, known as the band gap,
determines whether a material is a conductor, an insulator, or a semiconductor. In metals, the
valence and conduction bands are overlap, allowing electrons to move freely throughout the
material, resulting in high electrical conductivity. In insulators, the band gap is large enough
that there are no available energy levels for electrons to occupy, resulting in no electrical
conductivity.

In semiconductors, the band gap is small enough that electrons can be promoted from
the valence band to the conduction band with the addition of energy, such as heat or light,
resulting in intermediate levels of conductivity. The band structure of a crystal is determined
by the arrangement of its atoms in the lattice structure. The periodic nature of the lattice
structure gives rise to the formation of allowed energy bands, and the electronic properties of
the crystal are strongly influenced by the interactions between the electrons and the lattice. The

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study of electronic band structure is therefore critical in understanding the behaviour of a wide
range of materials, from metals and insulators to semiconductors and superconductors.

Figure 3 Electronic bands structure

The density of states (DOS) is the number of different states at a particular energy level that
electrons are allowed to occupy, i.e., the number of electron states per unit volume per unit
energy. The partial density of states (PDOS) is the contribution of a particular orbitals such as
s, p, d, f, etc in the total density of states.

The electronic band structure, total density of states (TDOS) and PDOS for PtSeTe, monolayers
were computed which are in Figure-5. From the analysis of the band diagram, the material
shows semiconducting nature with an indirect band gap of 1.10 eV. The maxima of valance
band located near to the Г-point, while the minima of the conduction band also located near
the Г-point for pristine PtSeTe ML. In addition, we investigate the PDOS and TDOS of the
monolayers. A significant contribution of electrons is observed in the valence band, primarily
from the Se-4p orbitals. The PDOS diagram suggests possible orbital hybridization near the

pg. 24
Fermi level in both the valence and conduction bands, particularly around -2 eV, -1.15 eV, and
1.75 eV energy levels.

Figure 4 Partial density of states of PtSeTe

pg. 25
Figure 5 Density of States of PtSeTe

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 Conclusions
In the framework of the first principles based DFT calculations which were carried out
by SIESTA code to compute the optimized geometric structural configurations, phonon
dispersion curves, electronic properties such as electronic band structure, total and partial
density of states for pristine and vacancy defected monolayer.

Our results show that PtSeTe is both thermodynamically and dynamically stable, as
indicated by its negative cohesive energy and the absence of imaginary frequencies in the
phonon spectrum. These findings indicate the structural stability of the PtSeTe monolayer and
suggest its potential as a viable candidate for synthesis. We have studied the electronic and
structural properties of the PtSeTe monolayer. In addition, we investigated the electronic band
structure and density of states of the Janus monolayer, which exhibits an indirect band gap of
1.10 eV.

Due to its indirect band gap, the charge carriers in PtSeTe possess longer lifetimes and
slower recombination rates. Therefore, this material holds promise for applications in solar
cells and photodetectors.

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 References
[1] Feynman, Richard P. (1960) There's Plenty of Room at the Bottom. Engineering and
Science, 23 (5). pp. 22-36.

[2] Prediction of a new graphene-like Si2BN solid-Antonis N. Andriotis, Ernst Richter, and
Madhu Menon, Phys. Rev. B 93, 081413(R)

[3] Bekyarova E,Itkis ME , Ramesh P, Berger C, Sprinkle M, De Heer WA, et al. Emerging
photoluminescence in monolayer MoS2. Nano Lett 2010; 10-1271-5.

[4] Siesta Webpage, Retrieved 30 November 2020, from [Link]

[5] J. Perdew, K. Burke, & M. Ernzerhof, (1996), Phys. Rev. Lett.,77(18),38653 88.(4)
[Link], & [Link],(1952)49(6),409

[6] Hohenberg, P., & Kohn, W. J. P. R. (1964). Density functional theory (DFT). Phys. Rev,
136(1964), B864.

[7] Monkhorst, H. J., & Pack, J. D. (1976). Special points for Brillouin-zone integrations.
Physical review B, 13(12), 5188.

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