Chapter Two

Theoretical study
2.1 Introduction
Molecular modeling methods in physics and theoretical chemistry are widespread
for examining many computational properties such as energies of molecules, molecular
geometry, electronic structure, electron and charge distribution, infrared (IR), ultraviolet
(UV), and nuclear magnetic resonance (NMR) spectra, physical properties, catalytic drugs,
and other molecular systems. Perhaps the best of these methods is the density functional
theory test (DFT) [31].
Because of the success of the DFT test in atomic and molecular physics issues and
solid state calculations, this method has proven successful even in nuclear calculations, so it is
a method approved by many physicists [33].
Theoretical physicists and chemists use four main methods in their calculations: they include
molecular mechanics methods, semi-empirical (SE) methods, ab-initio methods and density
functional theory methods. The key to theoretical physics is molecular quantum mechanics
[34].
2.2 Quantum mechanics theory

It is part of modern physics and is concerned with studying the behavior of matter,
including light at the atomic and subatomic levels. This theory tries to explain the behavior of
the atom and its basic components, while classical physics is concerned with studying the
phenomenal things and their mechanics, such as determining location, velocity, momentum,
and momentum. A property confined to objects, as waves do not have momentum, and this is
possible in classical physics, while this thing is not possible in quantum mechanics, because it
is not possible to determine the location of subatomic objects with high accuracy along with
their momentum at the same time, and this is confirmed by the principle of inaccuracy of
Heisenberg [35].
2.3  Heisenberg Uncertainty Principle
One of the most important principles of quantum theory was formulated by the
German theoretical physicist Heisenberg in 1927, which states that it is not possible to
calculate two measured characteristics of a quantum system with the same accuracy at the
same time [36].

2.4 Schrödinger equation

The Schrödinger equation is a partial differential equation that provides an
explanation of how the quantum numbers of a physical system change with time. Developed
by Austrian physicist Erwin Schrödinger at the beginning of the 19th century, this equation is
of great importance in quantum mechanics because it corresponds to Newton's second law in
classical physics , The time dependent form of Schrödinger equation is as the following
equation [37].
From a quantum point of view, the Schrödinger equation is similar to Newton's second law. It
is also a differential equation that describes how the physical body moves [38]. Then the
Schrödinger equation and Newton's laws were evaluated for time-dependent systems, where
the total energy (E) is equal to the sum of the total kinetic energy and energy latent [39].
E = KE (kinetic energy) + PE (potential energy) ...................(1)
And the kinetic energy of the electron can be calculated through the following equation [38] .
KE=(1/2)mv2=p2/2m ..........................(2)
where m is the mass of the particle, v is the velocity of the particle, and p denotes the
momentum of the particle. An electron moving in a field of charge Ze has a potential energy
of [40].

PE= -Ze2r -1 .....................(3)

where r is the distance between the electron and the nucleus and e is the unit of electronic
charge. As a result, the total energy of an electron is :
E= ( P2/2m) -Ze2 r -1 ......................(4)
a kinetic energy contribution and a potential energy function added together [39]
.

{
−
ℏ 2 2 Ze 2
2m
∇ −
r }
ψ (r )=Eψ (r )
...........................(5)

Where:
 : Plank constant (h) divided by 2 . and  : The wave function of an electron.

 2 :The Laplacian operator is a kind of operator (kinetic energy operator).

Eq. (7) denotes the Hamiltonian operator, denoted by the letter ^

H . Schrödinger

equation is written in condensed form as [41].

^
H Ψ (r)= E Ψ (r) ...............................(6)

The Hamiltonian operator with a large number of electron can be expressed in a similar
way. It is the sum of the kinetic energy operators of the nucleus and electrons, as well as the
potential energy operator denoted by the many Coulomb interactions by the following
equation [42]
N 2n 2n N 2n N
1 1 2 1
H =− ∑
T
∇ A − ∑ ∇ 2p + ∑ r −1
pd −∑ ∑ Z A r Ap + ∑ Z A Z B R AB
−1 −1
2 A MA 2 p p<d A p A <B ......
..(7)
Where MA is the mass of nucleus A , m electronic mass, ZA, ZB are the charges
on nuclei A and B, respectively, rpd is the distance between p and d electrons,
and RAB is the distance between nuclei A and B. The general form of
Schrödinger equation will be[43]
HT(1,2,…,N,1,2,..,n) Ψ(1,2,…,N,1,2,..,n)=EΨ(1,2,…,N,1,2,..,n) ...............(8)
WhereΨ(1,2,…,N,1,2,..,n) is the entire wave function for all particles in the
molecule and is the overall energy of the system.

2.5 Wave Function

The wave function Ψ cannot be seen physically, but it can be explained physically, as
the square of the wave function [Ψ] 2
represents the probability density of the particle being
studied within the coordinates of the site. Acceptable wave functions for a system must:

1. Orthogonal one to another.

2. Normalize.
3. Form a complete set.

Orthonormality refers to the property that wave functions have:

∫ Ψ ¿i Ψ j dx N =⟨ Ψ i|Ψ j ⟩ =δij ≡ {1, if i= j

0 , if i≠ j
.............................(9)

Completeness refers to the ability to create the "delta function," which is the
sharpest possible function of the unit area, from the whole set of eigen functions.
The energy of a wave function can be calculated using the Hamiltonian
operator's predicted value [44,45].

E=¿ ^
H>¿
∫ ¿
Ψ H^ Ψ dv
...................................(10)
∫ Ψ ¿ Ψ dv
The wave function Ψ describes the many-particle systems.

2.6 Hartree - Fock (HF) Approximation

When applying the Pauli exclusion principle in solving the Schrödinger equation for
many-electron atoms, molecules, or solids. The wave function becomes asymmetric. The
physicist Hartree was the first to derive the many-electron Schrödinger equations, and the
entire wave function, according to Hartree, can be approximated as a series of one-electron
wave functions [46] .
n
Ψ tot =∏ Ψ i (x ) ........................( 11)
i=1

When Hartree solved the non-time dependent Schrödinger equation, he did not take into
account the Pauli exclusion principle so Fock and Slater updated this method to include the
effect of electron exchange and the exclusion principle; So he used Slater's determinant, and
the wave function resulted, including systems consisting of n electrons, as shown below [47]

| |
Ψ 1 (x 1) Ψ 2 ( x 1) … Ψ n ( x 1)
1 Ψ 1 (x 2) Ψ 2 ( x 2) ⋯ Ψ n ( x 2)
Ψ ( 1,2 ,… , n )= ...................(12)
√n ! ⋮ ⋮ ⋱ ⋮
Ψ 1 (x n) Ψ 2 ( x n) ⋯ Ψ n ( x n)

Hartree-Fock equations, are a type of self-consistent field equation. These equations are
formatted as follows:
[ H core + ∑ ( 2 J j −K j ) ]Ψ i=∑ ε ij Ψ j i=1,…,n
j j ............................(13)
FΨ =∑ ε ij Ψ j i=1 , … , n ..............................(14)
j

Empirical wave functions are used to interchange potential integrals and differential equations
and to solve the N Hartree-Focke equations. Solving the n equations results in a new set of
wave functions. Then, the new wave functions are used to calculate a new set of possible
integrals. The cyclic approach is repeated for the estimated wave functions or potential
integrals to remain unchanged, because the final wave functions produce potential integrals,
which in turn produce identical wave functions within a given admission, at the equations.
( 16 ), this approach is known as the self-consistent field method [48,49].
2.7 Density functional theory ( DFT)
The quantum mechanical method of density functional theory (DFT) is frequently
used to study the electronic structure of many-electron systems in physics and chemistry. It is
presently one of the most important techniques for determining the ground state properties of
metals, semiconductors, and insulators [50].
Thomas Fermi's model provided the basis for density theory. In 1927, Thomas and Fermi
described the energy of an atom as a function of electron density, integrating that with
standard equations, nuclear, electron, and electron–electron interactions can be expressed in
terms of electron density [51]. The system is only affected by three coordinates, regardless of
the number of electrons in it [50]
N=∫ ρ ( r⃗ ) d ⃗r ...........................(15)

The ground state energy can be calculated by DFT, the ground state properties depend on the
electron density. The electronic density corresponds to the fine ground conditions of the
system when the total energy is low [52, 53].

2.8 Time-Dependent Density Functional Theory (TD-DFT)

The time-dependent density functional theory (TD-DFT) spreads the
important idea of the ground-state DFT which can be used to examine the
excited-state properties of a system in the presence of time-dependent potentials,
such as electric or magnetic fields. The influence of fields on molecules can be
studied with TD-DFT as an application for representative excitation energies,
oscillator strength, wavelength, molecular orbital character and electronic
transitions of the molecules[54-55].
The theoretical of TD-DFT based on the Runge-Gross theorem (R-G
theorem) in 1984. The R-G theorem explained the association between the time-
dependent external potential V^ ext . (⃗r ,t ) and ρ( r⃗ , t) of the system. R-G theorem
designated that when two external potentials V^ ext . (⃗r ,t ) and V^ 'ext . ( r⃗ , t )have
analteration of more than a time-dependent function, their own electron densities
ρ( r⃗ , t) and ρ ' ( ⃗r , t ) are also dissimilar[56-57].

Runge and Gross discussed how excited states are obtained using TD-
DFT. The starting point of studying time-dependent systems is the time-
dependent Schrodinger equation. The TD- DFT is straight related to the
∂
Schrodinger equation [iℏ ∂t Ψ ( r⃗ , t ) = ^
H Ψ ( r⃗ , t )] where the Hamiltonian is known to

be[58,59,60]:

^
H=Τ^ + V
^ elec . elec. + V
^ ext . ( r⃗ , t ) … … … … … … … … … … … .(16)

Here, ^
H consists of the kinetic energy operator Τ^ , electron-electron repulsion
^ ^ ^ (⃗r ) is
V elec . elec. (Coulomb operator) and the external potential V ext . ( r
⃗ ) .Where V ext .

given in the following operators:

N
^ ext . ( r⃗ ) =∑ V ext . ( ⃗r i , t )… … … … … … .(17)
V
i=1

The densities of the system rise from a fixed first stateΨ ( t 0 )=Ψ ( 0). The
first state, Ψ ( 0) , is arbitrary, it must not be the ground-state or some other eigen
state of the first potential V^ ext . (⃗r ,t 0 ) = V^ 0 (⃗r ).The R-G theorem indicates that there
exists an one-to-one correspondence between the time-dependent external
potentialV^ ext . (⃗r ,t ), and the time-dependent electron density ρ( r⃗ , t), for systems
developing from a fixed first many-body state. Translation to it, the density
determines the external potential, and next helps in obtaining the time-dependent
many-body wave functions[57,58].
 As this wave-function controls all observables of the systemas
animportant, the saying point is that all observables are functionals of ρ( r⃗ , t).
The statement of the theorem is the “densities ρ( r⃗ , t) and ρ' ( ⃗r ,t )evolving from the
same initial state Ψ ( 0) under the effect of two potentials V^ ext . (⃗r ,t ) and V^ 'ext . ( r⃗ , t )are
always different provided that the potentials differ by additional than a chastely
time-dependent function[58,59,61]:
^ (⃗r ,t )= V
V ^ 'ext . ( r⃗ , t )+ C ( t ) … … … … … … … … … … … .(18)
ext .

Where the C ( t ) allows increase to wave functions that are different only by
a phase factor exp ⁡(−iC ( t ) ), therefore, the same electronic density is stable. R-G
theorem states that the density is a functional of the external potential and of the
first wave function on the space of potentials differing by more than the addition
of C ( t ).

Hybrid Functionals 2.9

The hybrid exchange-correlation functionals occupy a privatesite in the

molecular applications of the DFT and nowadays it is very popular used in
computational physics and chemistry[62,63]. These functionals combine the
exchange-correlation GGA functionals and an exact exchange functional. The
most widely hybrid functional, B3LYP uses Becke’s1988 exchange functional (
E X ) and Lee-Yang-Parrcorrelation functional ( EC ) as gradient corrections to
B 88 LYP

the LSDA exchange and correlation functionals. The exchange-correlation term

of B3LYP is shown as in the following form[64,65,66,67]:

… … … … … . … .(19)
B 3 LYP LSDA HF B 88 LYP LSDA
E XC =( 1−a ) E X +a E XC +b E X +c E C + ( 1−c ) EC

Where the three parameters (a=0.20, b=0.72 and c=0.81), these values were
found by fitting the experimental data. The first parameter (a) specified the
amount of exact exchange, while (b) and (c) control the contribution of
exchange and correlation.
Basis Sets 2.10

A basis set in theoretical physical and chemistry is a set of

mathematical functions used to describe the shape of the molecular orbitals.
Both ab-initio and DFT methods employ basis sets to mathematically specify the
molecular orbitals in a system. Even though it is possible to create a basis set
from scratch, most calculations are done using existing basis sets. The accuracy
of the results is determined by the type of performing calculations and the
chosen basis sets. There are two types of basis sets, Slater-type Orbitals (STO’s)
and Gaussian-type Orbitals (GTOs)[68-69].

Slater-type Orbitals (STO) 2.11

The STO’s are exponential that mimic the exact eigen functions of the
hydrogen atom where in 1930 the physicist John C. Slater, who introduced
them. The STO’s can be defined in spherical polar coordinates as[70,71,72]:
STO n−1 −ξ r⃗
χ =N ⃗r e Y lm (θ , φ ) … … … … … ….. … .(20)

Where N is a constant of normalization, n represents a principal quantum

number, ξ is a constant related to the effective charge of the nucleus, r⃗ denotes
the distance of the electron from the  nucleus, Y lm ( θ ,φ ) denotes a spherical
harmonic and l , m are the orbital and magnetic quantum numbers, respectively.

Gaussian-type Orbitals (GTO) 2.12

The use of GTOs in electronic structure was first proposed by Boys in

1950. The GTOs can be written in terms of Cartesian coordinates as in the
following form[73,66,69]:
2

χ GTO =N xlx y ly z lz e−ξ r⃗ … … … … … … … … … ..(21)

Here;ξ denotes the orbital exponent that explained how compact (large ξ ) or
diffuse (small ξ ) is the resulting function. The r⃗2 dependence in the exponential
is a deficiency of the GTOs with respect to the STOs. The sum of angular
momentum lx , ly and lz determines the type of orbitals.
Additionally, some primitive Gaussian functions are diverse to give a
contracted Gaussian function (CGF) as in the following form[66,74]:
M
χ CGF
j =∑ C ij χ GTO
a … … … … … … … … … … . ( 22 )
i

Where M is the number of Gaussian primitives used in a linear combination and

C ij are the orbital expansion coefficients. The basis sets used in Gaussian are

classified as below:

Minimal Basis Sets and Split-Valence 2.12.1

The minimal basis set is the minimum number of basis functions χ

needed to define the ground states of the atoms in a molecule. A common
minimal basis sets are STO-nG, where n (n= 2 to 6) signified the number of
Gaussian primitive functions that include a single basis function[75,76].
Minimal basis sets typically give rough results that are poor for research class
magazine, but are much cheaper than their larger complements. For example the
minimal basis sets are the STO-2G, STO-3G and STO-6G[77,78]. In this type,
split-valence basis sets the inner-shell atomic orbitals are demonstrated by one
basis function and the valence orbitals are signified by two or more basis
functions split-valence basis sets employ more than one basis function of
variable orbital exponents for each valence orbital and only one basis function
for each core orbital. For example, the 6-31G basis set uses a set of six
primitives contracted to one basis function for each core orbital and a split-
valence of three and one primitive for the valence orbitals[70,73,79].

Polarization and Diffuse Functions 2.1.2.2

 Polarization functions are functions of higher angular
momentum such as d- and f-type functions for heavy atoms and p- and d-
type functions for hydrogen and helium atom[70]. Polarization functions are
used because they often result in more precisecalculated geometries and
frequencies. This increases the flexibility of the basis set by allowing the
shape of the orbital to become polarized in one direction. The inclusion of
polarization functions can be significant for systems in which hydrogen is
complicatedsuch as hydrogen-bonding and proton transfers since These will
allow the s orbital to become distorted from its regular spherical
shape[70,80].
The addition of polarization functions is indicated in brackets after the
reduction arrangement while wordy functions denoted by ‘+’. For instance, the
6-31++G(d, p) basis set includes a set of d-type functions on all heavy atoms
and p-type functions on hydrogen and helium. The first ‘+’ indicates that diffuse
s- and p-type functions are included on heavy atoms, while the second ‘+’
indicates that diffuse s-type functions have been included on hydrogen. Another
group of basis sets that are industrializedexactly for use in calculations that
include electron correlation. These basis sets are the correlation-consistent
polarized valence (double/triple) zeta basis sets, cc-pVXZ, where X denotes the
degree of splitting[70,79,81]. for heavy metals, the relativistic Effective-Core
Potentials (ECPs) such as Stuttgart Dresden triple zeta ECPs (SDD) basis set is
used. The types ofLos Alamos Nationwide Laboratory 2-double-zeta
(LANL2DZ) and SDD basis sets are powerfully recommended for heavy metals.
Scalar relativistic corrections are more rigorous than ECPs and spin-free
computes are not much more expensive[79,82].
Computations Properties 2.13
 The computation of molecular electronic properties in this study are
carried out by Koopmans theorem (KT). The description of the calculated
propertiesis shown as below.

Energy of HOMO, LUMO and Band Gap 2.13.1

HOMO and LUMO are two most significant of molecular orbitals,

where the HOMO denotes highest occupied molecular orbital and the LUMO
refers the lowest unoccupied molecular orbital. These orbitals are called the
frontier orbitals as they lie at the outmost boundaries of the electrons of the
molecules. The HOMO, which is the highest energy orbital containing electrons,
is the orbital acting as an electron donor. Inversely, the LUMO, is the lowest
energy orbital having space to accept electrons. The energy gap E gap regards the
difference of the energies between the HOMO and LUMO levels as[83,84]:

E gap =E LUMO−E HOMO … … … … … … … … … . … .(23)

HOMO and LUMO and their resultant energy gap did not only determine
the path the molecules interacts with other species, but their energy gap helps
label the chemical reactivity and kinetic constancy of the molecule. A molecule
with a small frontier orbital gap is more polarizable and is generally related with
a high chemical reactivity, low kinetic stability and it is also termed as a soft
molecule[72,84].

Total Energy, Ionization Potential and Electron Affinity 2.13.2

The total energy ET signifies the sum of total kinetic and potential
energy of the system, at the relax structure where the total energy of the
molecule must be at the lowest value because the molecule is at the equilibrium
position, which means the resulting of the real forces is zero[83,85].
The ionization potential (Ionization Energy I E ) for a molecule is the quantity of
energy needed to remove an electron from an atom or molecule and expressed as
the energy difference between the positive charged energy E+¿ ¿ and the neutral En
( I E =E+¿−E ¿). The HOMO and LUMO energy were also used to compute I E in the
n

framework of Koopmans theorem as in the following association[86-87]:

I E =−E HOMO … … … … … … … … .(24)

The electron affinity ( E) Aof an atom or molecule is the energy

change when an electron added to the neutral atom to form a negative ion and
En
expressed as the energy difference between the and the negative charged
E−¿¿ ¿
energy according to the following relative [101,102]. According to
Koopmans theorem, the HOMO and LUMO energies were also used to calculate
EA
:the as[85,86]

E A =−E LUMO … … … … … … … … . … .(25)

Chemical Potential Chemical Hardness and Softness 2.13.3

Within the plan of the DFT, one of the global amounts is chemical
potential ( x ), it measures the escapeetendency of an electronic cloud. It is a
constant, through all space, for the ground state of an atom, molecule or solid,
and equals the slope of the energy versus N curve at constant potential v (⃗r ):

x=
[ ]
∂E
v … … … … … … … … .(26)
∂ N (r⃗ )

Also, x is relatedexperimentallyto two known quantities, I E and E A , as in the

following relationship[79,87,88]:
1 1
X ≈ ( E HOMO + E LUMO ) ≈− ( I E + E A ) … … … … …..( 27)
2 2
The hardness (H ) is a measurement of molecule resistance to the change
or deformation and defined in the form[88]:

1 ∂X
H= ( ) … … … … ….. … .(28)
2 ∂ N V (⃗r )

In terms of I E and E A , the hardness is half of the energy gap between two frontier
orbitals[87,89]:
 I E −E A
H= … … … … … … … … .(29)
2

The hard molecule has a large energy gap. The theoretical meaning of
chemical hardness has been providing by the DFT as the second derivative of
electronic energy with respect to the number of electrons N , for a constant
potential V ( r⃗ )[88,89]:

H=
[ ] [ ]
1 ∂2 E
2 ∂ N2
=
V (⃗r )
1 ∂x
2 ∂N V (⃗r )
… … … … … … … .(30)

The soft molecules have a small energy gap and this means small
excitation energies to the various of excited states, their electron density changes
more simply than hard molecules, and due to that, soft molecules will be more
reactive than hard molecules. The electronic softness S is a property of
molecules that measures the degree of chemical reactivity. It is the inverse of H
[88,91]:

( ) ( )
2
1 ∂ N ∂N
S= = = … … … … … ..(31)
2H ∂E
2
V ( ⃗r)
∂K V ( ⃗r)

Electrophilic index and Electronegativity 2.13.2

The Electrophilic index is a measure of energy lowering due to maximal
electron flow between donor and acceptor. In which the Electrophilic index (ω)
given in the following form[92]:
x2
ω= … … … … … … … .(32)
2H
The Electrophilicity is built up from the electronic structure of
moleculesindependent of the nucleophilic. The electrophiles are species that
stabilize upon receiving on additional amount of electronic charge from the
environment[92,93].
The Electronegativity ( E N ) is a measure of the tendency to attract
electrons by an atom in a chemical bond and defined as the negative of the
chemical potential ( E N =−x ¿ in DFT and given as[86,94]:
 1
E N = ( I E + E A ) … … … … … … … … . ….( 33)
2
To evaluation the Electronegativity according to Koopmans theorem, it can be
defined as the negative value for average of the energy levels of the HOMO and
LUMO[86,94]:
−1
EN=
2
( EHOMO −E LUMO ) … … … … … … … … … … … .(34 )

Molecular Polarizability and Total 2.13.3

Dipole Moment

The electric dipole polarizability is a measure of the linear response of the

electron density in the presence of an electric field F and it signifies a second
:order difference in energy[95,96]

( )
2
∂ E
∝a ,b = ( a , b=x , y , z ) … … … … … … ...(35)
∂ Fa∂ Fb

The polarizability⟨ ∝ ⟩is calculated as the mean value and given as in the
following equation[95]:
1
⟨ ∝ ⟩= ( ∝ XX +∝ yy +∝ zz ) … … … … … … ….. … .(36)
3
Here ∝ XX , ∝ yy∧∝ZZ denoted the eigen values of the polarizability tensor.
The dipole moment ( P) signifies the first derivative of the energy with respect to
an applied electric field. It is a measure of the asymmetry in molecular charge
distribution. The unit Measurement of dipole moment is Debye (1 Debye =
Coulomb .meter ). In quantum mechanical account of dipole moment,
−30
3.336 ×10

the charge is a continuous distribution that is a function of ( r⃗ ). The total dipole

moment is given by the following equation[97,96]:

Fermi Energy 2.15

 Fermi energy, the fundamental variation principle in DFT, is used to
measure the escaping trend of a cloud of electrons. It is a constant through all
space and can be calculated according to the following equation [98]

∂E
EF = [ ∂ N ] 𝑣 (r) .......................................( 37).

Where E is the energy and N is the number of electrons.

Experimentally, Fermi energy EF is correlated with E HOMO and E LUMO , as in

the following equation [99] .

1
EF ≈ 2 (E HOMO + E LUMO ) .....................................(38)

2.16 Geometrical structures

All molecules possess geometry, characterized by:

1. The number and kinds of atoms.

2. Bonds' number and types.

3. Bond lengths that are relevant r : 0 ≤ r ≤ ∞ .

.Bond aspect that is relevant θ : -180º ≤ θ ≤ 180º (units of degrees) .4

Geometry optimization is a physical chemistry computation that determines the

lowest energy or most relaxed conformation of a molecule. The approach is an
iterative process in which the molecular shape is changed slightly at each stage
and the energy of the molecule is compared to the preceding cycle. The
computer gently pushes the molecule in order to achieve the most relaxed
condition possible. Calculates the energy, then pushes it a bit further till the
lowest energy is determined. At the ideal geometry, the molecule's energy
minimum is discovered[99].
2.17 Open-circuit voltages
The open-circuit voltage (VOC) is considered to be an important property that
pointed gain voltaic for proposed nano-system. The VOC can be calculated as shown in Eq. :

VOC = | (HOMO (Doner) | –| LUMO (Acceptor) | - ∆........................(39)

where ∆ is an empirical value ranging from 0.3 to 0.5 eV

| HOMO(D) | - | LUMO (A) | represents the doner/acceptor effective energy gap .it should
be noted that the value ∆ depends on the choice of doner/acceptor system. a typical value of
∆ = 0.3 eV and its value may be greater or smaller in different OSCs [100].
The open circuit voltage is the maximum voltage that the solar panel can produce with
no load on it (i.e. measured with a multi meter across the open ends of the wires attached to
the panel). If two or more panels are wired in series it will be Voc of panel 1 + Voc of panel
2, etc. The voltage is generally highest mid-morning as the sun rises rapidly and the panel
temperature is still quite low.
The Voc + approx 3.5 per cent must be less than the maximum solar voltage permitted by the
solar-charge controller. Some controllers shut down if it’s exceeded, while some may
continue to operate but the lifespan of the controller could be compromised or it may result in
immediate destruction of the device . [101].

2.18 Electrons injection process

The valence band is an energy band that lies below the conduction band. When the
valence band is filled to the brim with electrons and the conduction band is devoid of any
electron, the material loses its electrical conductivity. Therefore, there must be some voids
within the valence band to conduct electricity, or the presence of some electrons in the
conduction band. One of these spaces is called an electron hole.
In order for an electron to move from the valence band to the conduction band it needs energy
at least equal to the band gap. In order to fall from the conduction band to the valence band, it
must lose energy at least equal to the bandgap in the form of light (photon) or heat (phonon).
This process is called (electron injection). If the bandgap is direct, the electron releases its
energy in the form of a photon. If the bandgap is indirect, release its energy in the form of a
phonon. The transfer of electrons between the conduction and valence bands is used in several
applications, the most important of which are the solar cell, lasers, masers, and the luminous
diode [102].
and this process can be calculated through the following equation:

∆Ginjuct = E*- ECB ( TiO2 )

where E* represents the energy of the excited state
E*= Edye - ∆E , where = -HOMO and ∆E= 1240/ λ max

ECB ( TiO2 ) = 3.9 [100].

then ∆Ginjuct = -HOMO -(1240/ λ max) -3.9 .....................(40) [123].

Where the constant (1240) is the net product of Planck's constant (6.62607015 x 10-34 m 2 kg
/ s) and the speed of light (3 x108 m / s) divided by the wavelength in units of nanometers and
after abbreviating the units and converting the unit of the resulting quantity into electron volts
we get this formula .

2.19 Light Harvesting Efficiency (LHF)

One of the important parameter for design efficient photonic device is light harvesting
efficiency (LHF), it
proportional directly with oscillation strength value[98], this can have been computed by
equation :
𝐿𝐻𝐸 = 1 − 10−𝑓 .....................(41)
Where ( f ) represent oscillation strength associated with maximum wave length of absorption
[103].

Electronic Transitions 2.14

The absorption of UV or visible radiation agrees to the excitation of
outer electrons. There are three types of electronic transition which can be
consideredas the first are the transitions involving p, s, and n electrons, the
second are the transitions involving charge-transfer electrons and the third are
the transitions involving d and f electrons.
When an atom or molecule absorbs energy, electrons are promoted from their
ground state to an excited state. In a molecule, the atoms can rotate and vibrate
with respect to each other. These vibrations and rotations also have separate
energy levels, which can be considered as existence packed on top of each
electronic level.
Absorption of ultraviolet and visible radiation in organic molecules is limited to
certain functional groups (chromophores) that contain valence electrons of low
excitation energy. The spectrum of a molecule containing these chromospheres
is complex[104]. The Possible electronic transitions of p, s, and n electrons are
shown as in Figure (2.1).

.Figure 2.1:The electronic transitions of p, s, and n electrons [104]

Infrared IR-Spectrum 1 2.14
The infrared IR spectrum is an electromagnetic radiation. The N-atoms
system absorbs amount of energy will oscillate with three degrees of freedom
for both translation and rotation, and (3N-6) degrees of freedom for vibration for
ring molecules. The vibration of a molecule is modeled by normal modes of
simple harmonic oscillator to absorb and emit the energy. The normal
oscillations that are associated with changes in dipole moments are active and
they appear in the range of infrared radiation.
The oscillations of a system have two types of bands, fundamental and
unfundamental oscillation bands. The fundamental bands are accompanied with
more changes in dipole moments and they are classified according to high
intensity as stretching, distortion, wagging, twisting, rocking and bending
oscillations. While unfundamental bands, overtone and hot bands which have
low intensity[80]. The vibration analysis is valid only when the first derivative
of the energy with respect to displacement of the atoms is zero[105].

UV- Visible radiation 2.14.2

The excitation of electrons in both atoms and molecules from lower to

higher energy levels is connected to the absorption of visible (Vis) and
ultraviolet (UV) light. Because matter's energy levels are quantized, only light
with precisely the right amount of energy can drive transitions from one level to
the next. Ultraviolet radiation is a type of radiation that exists just below the
visible spectrum of light. It has a range of wavelengths from 100 to 400
nanometers , While the visible spectrum extends between 390 to 710 nm
[104].Specific compounds absorb UV or visible rays. Different molecules are
capable of absorbing different wavelengths of light. Within the molecule, an
absorption spectrum should show a range of absorption bands that correspond to
the structural groups[106]

The Software 2.15

All calculations in this study have been performed by using the Gaussian
09package of Programs, GaussView 5.0.8, Gauss Sum 3.0 and other assistant
programs.These programs are described as below:
Gaussian 09 (G09) Program 2.15.1
The Gaussian program is acomputational software package initially
published by John Pople in 1970. Gaussian program is a very high-end quantum
mechanical software package. The “09” mentions to the year 2009 in which the
software was published[107].
Gaussian is capable of running all of the major methods in molecular
modeling, including molecularmechanics,ab-initio, semi-empirical, HF and
DFT. Moreover, excited state computes can be done by different methods in this
program[108].
The name originatesGaussian comes from the use of the Gaussian Type
Orbitals that Gaussian's originator, John Pople, used to try to overcome the
computational difficulties that get up from the use of Slater Type Orbitals. A
number of researchers, such as S.F. Boys and Isaiah Shavitt, Pople, quite
brilliantly, recognized that the (relatively) simple, substitution of a series of
Gaussian functions for the Slater function, would greatly simplify the rest of the
calculation of the Schrödingerequation. Pople (1998) was awarded the Nobel
Prize in chemistry (along with Walter Kohn) for this work[107,108].
Gauss View Program 2.15.2
Gauss View was designed to import the input files for the Gaussian
program and also used to prove the output files for Gaussian program in the
dimensional photo, Gaussian view which not used as calculation program, but it
is simplicity the work on Gaussian program and supply the users three major
advantages.First: enable the user to draw the molecules including the big one,
also enable the rotation, transferring and changing it size easily and the mouse.
Second:Gaussian view permits to achieve many of the Gaussian calculation,
making the complex input preparation for the routine work and the advanced
method.Third: Gaussian view permits the inspection of Gaussian calculations
results using variety of geometrical techniques and this involved the balanced
molecular patterns electronic density surfaces[107,108].

Gauss Sum 3.0 2.15.3

The Gauss Sum 3.0 is a software application recorded by Noel O'Boyle.

Gauss Sum 3.0 uses the plotting program (Gnuplot17) for picture graphs. The
Gauss Sum is  that can examines the output of widely computational physics and
chemistry program (such as Gaussian 09 Program)[107,109].
 Gauss Sum can get ready more information such as a geometry
optimization, plot the density of states (DOS) spectrum, source information on
the UV-Vis. Transition states, scheme the UV-Vis spectrum and the circular
dichroism spectrum, abstract data on IR and Raman vibrations and plotting the
IR and Raman spectra, which may be scaled using general or individual scaling
factors [110] .