Assignment # 1: Computational Modelling of Materials

Submitted to: Dr. Fouzia Perveen Malik

Submitted by: Urooj Rasool
Registration No.: 00000535761
Dated: 04-03-2025
PhD Energy Systems Engineering
U.S.-Pakistan Center for Advanced Studies in Energy (USPCAS-E)
National University of Sciences & Technology (NUST), H-12, Islamabad.
Q:1. Explain the fundamental principles of DFT and why it is widely used in computational
materials science.

1. Density functional Theory

Like ab initio and SE calculations, density functional calculations (often called density functional theory
(DFT) calculations) are based on the Schrödinger equation. However, unlike the other two methods, DFT
does not calculate a wavefunction, but rather derives the electron distribution (electron density function)
directly [1]. The basis for DFT is the Hohenberg-Kohn theorem. The wave functions can be obtained by
solving the time-independent Schrödinger wave equation for the N-electron system [2].

ĤΨ=EΨ

^ + v^ +Û ¿ Ψ = E Ψ
(T 1

[∑ ( ) ]
N 2 N N
−h 2
∇ + ∑ V ( r i ) + ∑ U ( r i , r j ) Ψ =EΨ
i 2 mi i i<j

(a) The Hohenberg-Kohn theorem

Density functional theory is based on the two Hohenberg-Kohn theorems, which state that:

Theorem I:

“Any ground state property of a molecule is a functional of the ground state electron density function”,
e.g., for the energy:

E0 = F [ρ0] = E [ρ0] 2

Theorem II:

“Any trial electron density function will give energy higher than (or equal to, if it were exactly the true
electron density function) the true ground state energy”. The second theorem can thus be stated:

Ev [ρt] ≥ E0 [ρ0] 3

In DFT molecular computations the electronic energy from a trial electron density is the energy of the
electrons moving under the potential of the atomic nuclei. This nuclear potential is called the “external

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potential”, apparently because the nuclei are “external” if we concentrate on the electrons. This nuclear
potential is designated v(r), and the electronic energy is denoted by E v = Ev [ρ0] (meaning “the Ev
functional of the ground state electron density”) [1].

(b) The Kohn-Sham Equations

The success of modern DFT approaches is based on the concept by Kohn and Sham that the electron’s
kinetic energy should be derived using an auxiliary set of orbitals utilized for characterizing the electron
density [2]. The Kohn-Sham equations are obtained by differentiating the energy with respect to the KS
molecular orbitals. It gives exact energy, but only if we know the density function ρ 0(r) and the exchange-
correlation energy functional EXC[ρ0] [1]. The Kohn-Sham equation can be written as:

h^ Ψ =E Ψ
ks ks ks ks
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Where, h^ ks is the Kohn-Sham operator.

Exchange correlation function

Various DFT approaches can be differentiated based on the choice of functional form for the exchange
correlation energy. The two most popular exchange correlation functional approximations are described
below:

i) Local Density Approximation

In the Local Density Approximation (LDA) it is assumed that the density is slowly varying function so,
locally it can be treated as a uniform electron gas [2]. In case of LDA the exchange energy is given by:

E xc [ ρ ] = ∫ ρ ( r ) E xc ( ρ ( r ) ) dr
LDA unif
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Where, ρ is the electronic density, and

Exc is exchange correlation energy per particle.

ii) Generalized Gradient Approximation

In generalized gradient approximation (GGA) exchange-correlation energy functional E XC utilize both the
electron density and its gradient, the first derivative of ρ with respect to position, (∂/∂x + ∂/∂y + ∂/∂z)ρ =
∇ρ) [1]. In case of GGA the exchange energy is given by:

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 E xc [ ρ ] = ∫ d rρ ( r ) E xc ( ρ ( r ) , ∇ ρ ( r ) )
GGA 3 GGA
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There are several functionals within the GGA family that have been constructed depending on how the
gradient of the density ρ (r) has been increased. The most popular functionals are Perdew and Wang
(GGA-PW91), Perdew, Burke and Ernzerhof (GGA-PBE) and Becke, Lee, Yang, and Parr (GGA-BLYP).

Figure 3.1: Schematic Representation of computational chemistry Methods

2. DFT in Computational Material Science

Density Functional Theory (DFT) is widely used in computational materials science because it provides a
balance between accuracy and computational efficiency when studying the electronic structure of
materials [3]. Here are the key reasons why DFT is so popular:

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 i) Accuracy vs. Computational Cost

DFT provides reasonably accurate results for ground-state properties of materials while being
computationally feasible compared to more expensive wavefunction-based methods like Coupled
Cluster (CC) or Configuration Interaction (CI). Unlike classical force-field methods, DFT incorporates
quantum mechanical effects, making it more reliable for predicting material properties [4].

ii) Predictive Power for Material Properties

 DFT can accurately predict a wide range of properties, including:

o Electronic structure (band gaps, density of states)

o Structural properties (lattice parameters, bond lengths)

o Mechanical properties (elastic constants, bulk modulus)

o Thermodynamic properties (formation energies, phase stability)

o Electrochemical properties (redox potentials, reaction mechanisms)

This makes DFT essential for designing new materials for batteries, catalysts, semiconductors, and
more.

iii) Advancements in Exchange-Correlation Functionals

The accuracy of DFT depends on the choice of exchange-correlation (XC) functionals. Over time,
improved functionals like GGA (PBE), meta-GGA, and hybrid functionals (HSE06, B3LYP) have
enhanced predictive capabilities. For strongly correlated materials, DFT+U and DFT+DMFT approaches
provide better accuracy [5].

iv) Efficient Computational Implementations

DFT is implemented in powerful software packages such as VASP, Quantum ESPRESSO, CASTEP,
Wien2k, Gaussian, and DMol³. Parallel computing and GPU acceleration further enhance its efficiency.

v) Integration with Experimental Studies

DFT supports X-ray, spectroscopy, and electrochemical experiments by providing insights into
electronic structure and reaction mechanisms. It helps interpret XPS, Raman, IR, and EPR spectra,
making it indispensable for materials characterization [6].

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References

1. E. Lewars, COMPUTATIONAL CHEMISTRY Introduction to the Theory and Applications of

Molecular and Quantum Mechanics, vol. 13, no. 1.
2. F. Jenson, Introduction to Computational Chemistry. 2007.
3. Lee, J.G. (2016). Computational Materials Science: An Introduction, Second Edition (2nd ed.).
CRC Press.
4. Neugebauer, J., & Hickel, T. (2013). Density functional theory in materials science. Wiley
Interdisciplinary Reviews: Computational Molecular Science, 3(5), 438-448.
5. Hafner J, Wolverton C, Ceder G. Toward Computational Materials Design: The Impact of
Density Functional Theory on Materials Research. MRS Bulletin. 2006;31(9):659-668.
6. Landers, J., Gor, G. Y., & Neimark, A. V. (2013). Density functional theory methods for
characterization of porous materials. Colloids and Surfaces A: Physicochemical and Engineering
Aspects, 437, 3-32.