Computational and Theoretical Chemistry 1203 (2021) 113349

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Computational and Theoretical Chemistry

journal homepage: www.elsevier.com/locate/comptc

Electro-optical and charge transport properties of chalcone derivatives

using a dual approach from molecule to material level simulations
Rao Aqil Shehzad a, Shabbir Muhammad b, c, *, Aijaz Rasool Chaudhry d, Soichi Ito e,
Javed Iqbal a, *, Muhammad Khalid f, Zouhaier Aloui g, h, Hong-liang Xu i
a
Department of Chemistry, University of Agriculture Faisalabad, 38000 Faisalabad, Pakistan
b
Department of Physics, College of Science, King Khalid University, Abha 61413, P.O. Box 9004, Saudi Arabia
c
Research Center for Advanced Material Science (RCAMS), King Khalid University, Abha 61413, P.O. Box 9004, Saudi Arabia
d
Deanship of Scientific Research, University of Bisha, Bisha 61922, P.O. Box 551, Saudi Arabia
e
Institute for Molecular Science, 38 Nishigo-Naka, Myodaiji, Okazaki 444-8585, Japan
f
Department of Chemistry, Khwaja Fareed University of Engineering & Information Technology, Rahim Yar Khan 64200, Pakistan
g
Department of Chemistry, College of Science, King Khalid University, Abha 61413, P.O. Box 9004, Saudi Arabia
h
Laboratoire de Chimie des Matériaux, Université de Carthage, Faculté des Sciences de Bizerte, 7021 Zarzouna, Tunisia
i
Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, Jilin, People’s Republic of China

A R T I C L E I N F O A B S T R A C T

Keywords: In this study, three chalcone derivatives with a basic skeleton of [1,100-biphenyl]-4-yl)-3-(3-nitrophenyl)prop-2-
Chalcone derivatives en-1-one are investigated. The basic skeleton was modified with the addition of three-terminal groups including
Dielectric Function hydrogen (1), methyl (2), and methoxy group (3). Using CASTEP Module, the optoelectronic properties are
Extinction coefficient
evaluated. The solid-state geometries of these systems are explored within the periodic boundary conditions
Refractive Index
Electronic coupling
(PBC). Among these systems, system 3 is found much better in terms of electron transport and optical properties
such as dielectric function, absorption, conductivity, reflectivity, loss function, and refractive index. System 3
showed a higher dielectric function value about 3.7 at 1.8 eV thereby absorption 6.9 × 104 cm− 1 at 300 nm and
conductivity 1.2 fs− 1 at 3.5 eV in the (0 0 1) plane. Furthermore, system 3 exhibited a high reflectivity and loss
function in the (0 1 0) plane. Electronic band structure, the density of state, and electronic coupling analysis also
reveal that system 3 has a potential application in charge transport devices. The study of electronic couplings that
dominate the slowest electron hopping in a potential conductive path is roughly four to ten times larger for the
holes than for the electrons. The transport pathways in systems 1 and 2 are 2D, while 1D in system 3. The
bottleneck rate for electron transport is expected to be ~25 faster for system 3 than the other systems. This
system 3 shows an excellent potential both at molecular and bulk levels for efficient charge transport material.

1. Introduction using both experimental and theoretical approaches that exhibited an

The current attention of researchers is on the optoelectronic prop­
erties of the chalcone derivative that has applications in medicine and
modern electronics, including optical communication and integrated
circuits [1–4]. There are various kinds of semiconductors materials that
are of great interest due to their applications in different internet op­
erations, calculators, and solar cell technology [5,6]. These materials are
known for their low manufacturing cost, durability, and applications in
integrated circuits and various sensors operations [7–10]. Maidur et al.
[11] reported the nonlinear optical properties of the crystalline chalcone
derivative 3-(4-methoxyphenyl)-1-(4-nitrophenyl)prop-2-en-1-one
excellent potential for their use in the optical devices. The first inorganic
nonlinear optical molecule was reported in 1994 by Perry et al. [12] that
had many shortcomings. Later, different molecules are reported that
were much better than the previous materials. For example, inorganic
compounds like Group IVA elements Si, Ge, and their different chemical
combinations were utilized for the construction of highly efficient op­
tical devices [13,14]. Chen et al. [15] reported aromatic diimides to
achieve enhanced optoelectronic properties. Such organic molecules are
of great importance due to their low costs and commercial availability.
In previous studies, it is reported that thermal fluctuation reduces the
charge transfer properties of organic semiconductor molecules, so

* Corresponding authors at: Department of Physics, College of Science, King Khalid University, Abha 61413, P.O. Box 9004, Saudi Arabia (S. Muhammad).
E-mail addresses: mshabbir@kku.edu.sa (S. Muhammad), javed.iqbal@uaf.edu.pk (J. Iqbal).

https://doi.org/10.1016/j.comptc.2021.113349
Received 25 March 2021; Received in revised form 20 May 2021; Accepted 26 June 2021
Available online 30 June 2021
2210-271X/© 2021 Elsevier B.V. All rights reserved.
R.A. Shehzad et al.
π-stacking in different arrays like one dimensional (1D) and two
dimensional (2D) helped to mimic the delinquency of charge transfer
applications [16]. Electronic coupling (EC) is an essential parameter to
evaluate the intrinsic properties of the adjacent molecules. In this re­
gard, transfer integral values of rubrene were elaborated using EC [17].
Newton and Marshall D [18] also studied the EC in the long-range
transfer of electrons using quantum mechanics that enable studying
the properties of the complex system.
Over time, new materials were introduced to attain the desired re­
sults, such as metal–organic and polymer materials. Organic molecules
are considered the best choice due to the ease of modification in their
chemical structures and low processing cost [19,20]. Previously,
Mohana et al. [21] reported an organic molecule named pyrrolidinium
2-carboxy 6-nitrophthalate (PY3N) and investigated its different
photochemical, optical, and spectral properties. Many articles are re­
ported on fullerenes, non-fullerenes, push–pull groups, electron donors,
and acceptor moieties to achieve different applications such as high
power conversion efficiency in photovoltaics [22]. Also, some naturally
occurring molecules reported exhibiting biological and nonlinear
response, such as cinnamic acid and its derivatives reported by Hu and
co-workers [23]. For example, the shelf life of Agaricus bisporus (mush­
rooms) is enhanced using 4-methoxy cinnamic acid. A series of organic
molecules such as aryloxypropanolamines and its derivatives are of
great interest in medicine due to their unique properties like decreased
blood glucose level [24,25]. To get large electron mobilities and inter­
molecular interactions, π-stacking is an important strategy [26]. In this
regard, three systems are very important such as (E)-1-([1,100-
biphenyl]-4-yl)-3-(3-nitrophenyl)prop-2-en-1-one (system 1), (E)-1-
(400-methyl-[1,100-biphenyl]-4-yl)-3-(3-nitrophenyl)prop-2-en-1-one
(system 2) and (E)-1-(400-methoxy-[1,100-biphenyl]-4-yl)-3-(3-nitro­
phenyl)prop-2-en-1-one (system 3 that is similar to PY3N). These sys­
tems have shown significant properties in many areas including
biological operations where these derivatives act as antioxidants.
Chalcone derivatives also show great potential as organic optical and
photovoltaic materials [27–29]. The crystal structures have been
documented of these systems (system 1–3) [30–32].
The main concern of the current study is to measure the optoelec­
tronic properties of pre-investigated chalcone derivatives (system 1–3).
These molecules are important in terms of anti-inflammatory, antimi­
crobial, antifungal, and chemo-preventive activities [33,34]. Their
nonlinear optical polarizabilities were also analyzed that was quite
higher as compared to other chalcone derivatives using two approaches
computationally and experimentally [11]. But detailed optical proper­
ties of these chalcone derivatives are not reported yet. In the light of the
above literature, the centerpiece of our current work is to measure the
chalcone derivatives (system 1–3) in terms of its optical properties such
as dielectric function, conductivity, reflectivity, absorption, etc.
Furthermore, electronic band structure, the density of state (DOS) and
electronic coupling of chalcone derivatives are also evaluated to get
further insights into charge transfer properties.
2. Computational details
All the calculations were performed at two levels i.e. at molecular
and bulk levels. All the single molecular level calculations were per­
formed using Gaussian 16 suite of programs while for bulk-level calcu­
lations, CASTEP 19.1.1. [35] is used in the present investigation. The
selected bulk systems (1–3) were optimized using the Broyden-Fletcher-
Goldfarb-Shanno (BFGS) method. The bulk-level calculations were
performed to determine optical properties using the functional Perdew-
Burke-Ernzerhof (PBE) implanted in CASTEP [36,37]. The CASTEP
program within PBC is based on the pseudopotential parameters, Pulay
density-mixing scheme, and cut-off parameters of plane-wave basis set
[38]. The following lattice parameters were used as a = 17.655 Å, b =
6.146 Å, c = 30.023 Å, α = γ = 90◦ and β = 99.9◦ with 320.94 nm3 cell
volume for the 3D monoclinic system 1. The 3D monoclinic lattice
2
Computational and Theoretical Chemistry 1203 (2021) 113349
parameters of system 2 were used as a = 17.821 Å, b = 6.163 Å, c =
32.357 Å, α = γ = 90◦ and β = 103.17◦ with 346.05 nm3 cell volume and
3D triclinic system 3 has 176.26 nm3 cell volume with lattice parameters
as a = 10.192 Å, b = 10.873 Å, c = 16.967 Å, α = 97.93◦ , β = 93.71◦ and
γ = 107.73◦ . The sampling of Brillouin Zone (BZ) was done by imple­
menting reciprocal space approximated using the Monkhorst–Pack
scheme. The k-point set was selected as a fine mesh with (2 × 2 × 2)
values with a standard grid size of 1.5. An optimized cut-off energy of
300 eV for plane-wave expansion was used with Precise fast Fourier
transform (FFT) with the five largest prime factors [42]. Motion plan­
ning (MP) grid size for SCF calculation was (1 × 2 × 1) for three systems.
For these molecular crystals, the Broyden–Fletcher–Goldfarb–Shanno
hessian modified scheme (BFGS) was being used as a minimization
method, with the Self-consistent field (SCF) [39]. Pseudo atomic
calculation were performed for H: 1s1; C: 2s2, 2p2; N: 2s2, 2p3 and O: 2s2,
2p4. Meanwhile, the total energy/atom convergence tolerance was 2 ×
10− 6 eV/atom and Eigen energy convergence tolerance was 1 × 10− 6
eV. Some mathematical equations assist the calculation of optical
properties. For example, dielectric function (ε) is the base having real
(rε1) plus imaginary (iε2) parts for other optical properties that include
reflectivity R(ε), [40] extinction coefficient k(ε), refractive index n(ε)
[41] and energy loss function L(ε) as given below [42,43]:
( )[√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ ]12
1
k(ε) = √̅̅̅ ε1 (ε)2 + ε2 (ε)2 − ε1 (ε) (1)
2
⃒√̅̅̅̅̅̅̅̅̅̅2 ⃒
⃒ ε(ε) − 1⃒2
⃒ ⃒
R(ε) = ⃒√̅̅̅̅̅̅̅̅̅̅ ⃒ (2)
⃒ 2 ⃒
ε(ε) + 1
( ) √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
1 [ ]12
n(ε) = √̅̅̅ ε1 (ε)2 + ε2 (ε)2 + ε1 (ε) (3)
2
ε2 (ε)
L(ε) = (4)
ε1 (ε)2 + ε2 (ε)2
Electronic coupling matrix elements were evaluated in a molecular
cluster composed of twelve molecules. Geometries of molecular clusters
are taken from experimental X-ray structures [30–32]. The PBE0 xc-
functional [44] and 6-31G* [45] basis set was used for the electronic
coupling evaluations. These electronic coupling calculations were per­
formed using the non-orthogonal Green’s function method described in
the previous studies [46]. The HOMO and LUMO orbitals of the mole­
cules are obtained from block diagonalization of the monomer sub­
space’s cluster Fock matrix. These monomer orbitals are used for the
basis of electronic coupling calculations. The rest of the orbitals are also
used in the electronic coupling calculations, using them as “bridge“
orbitals. The Lowdin orthogonalized orbital representations character­
izes the total electronic couplings. The Fock matrix is obtained from the
neutral ground-state electron density of a cluster.
3. Results and discussion
3.1. Solid-State geometries of systems 1, 2 and 3
The entitled molecules are quite similar except the terminal groups
which are hydrogen, methyl, and methoxy in systems 1, 2, and 3,
respectively, as given in Fig. 1. These systems were optimized using the
experimental crystal data to predict the optical and electronic proper­
ties. The computed results of these optimized geometries were compared
with the experimental geometries and expressed in Fig. 2. After careful
analysis of these systems, it is observed that the computed bond lengths
are comparable to the experimental bond lengths. For example, the
computed bond length of the nitro group in system 1 is 1.26 Å (in O1-N4-
O2), while the experimental bond length is 1.22 Å. There is a small
difference in these computed and experimental values which is about
R.A. Shehzad et al.
Fig. 1. The representation of molecular structures for studied chemical systems
1–3. The general molecular structure of the entitled molecule.
0.04 Å. However, the terminal carbon-hydrogen (C23-H38) bond length
varies significantly. For example, the computed bond length is 1.09 Å
which is higher than the experimental value of 0.93 Å. Similarly, in
system 2, there is a small variation in the computed and experimental
data except in the terminal methyl group. The calculated bond length
between C26 with adjacent hydrogen is 1.10 Å, whereas 0.96 Å is the
reported experimental value. In system 3, there is no major difference in
the computed and experimental bond lengths, i.e. O37-N39-O38 has a
bond length of 1.22 Å while the bond length between carbon-hydrogen
in the methoxy group is 0.96 Å. Overall the computed results resembled
the reported experimental values that would be useful to predict their
properties with more precision.
3.2. Dielectric function
Dielectric function is a substantial factor in defining the properties
since it plays a major role in charge screening, capacitance, and storage
applications [47–49]. The components of dielectric functions are
Fig. 2. The solid-state geometries of the compounds 1, 2 and 3 within PBC. The bond lengths in parenthesis are their respective experimental single crystal structures
as given in angstrom (Å).
3
Computational and Theoretical Chemistry 1203 (2021) 113349
computed using three directions involving x, y, and z-axis (i, j, and k) for
Miller indices (hkl). Our system 1 showed the maximum value of 3.2 for
the real dielectric function in the (1 0 0) plane while the lowest value of
1.9 eV was observed in the (0 1 0) plane. In system 2, the highest value of
dielectric function was observed in the plane (0 0 1) which is 1.8 eV,
whereas the lowest values were obtained for the (1 0 0) plane with an
energy range of 3.5–4.5 eV. Similarly, system 3 in the (0 0 1) plane
exhibited the maximum dielectric value of 3.7 at about 1.8 eV. However,
the (1 0 0) plane is not varied as compared to other planes. After careful
analysis, it is observed that system 1 is quite different from systems 2
and 3 as the plane (1 0 0) is dominant in system 1, while plane (0 0 1) is
leading in systems 2 and 3, which are shown in Fig. 3. Among these
systems, only system 3 in the (0 0 1) plane exhibited the highest
dielectric function values than systems 1 and 2. From the above dis­
cussion, system 3 is a better candidate with a high capacity to store
charge if used in the capacitors.
3.3. Absorption and conductivity
Throughout physical chemistry, light absorption links with the
excitation of atoms, particles, or charging species from the ground to an
excited state and often responsible for electronic conduction [50]. The
maximum computed absorption of system 1 is found 5.2 × 104 cm− 1 in
(0 0 1) plane, while the lowest absorption exhibited by the (1 0 0) plane
with a value of 3.6 × 104 cm− 1 in the range of 380–400 nm. This ab­
sorption range is also useful for the construction of solar systems
[51,52]. Absorption towards a longer wavelength is useful to absorb
most of the visible light to excite the electron. Similarly, system 2
showed the same behavior, which indicated that there is no major
contribution of the methyl group in the absorption. However, system 3
R.A. Shehzad et al.
Fig. 3. The dielectric function of the entitled systems.
showed more intense peaks with strong absorption as compared to other
systems. For example, system 3 has maximum absorption approaching
6.9 × 104 cm− 1 at about 300 nm in the (0 0 1) plane, while system 3
absorption is relatively low, i.e., 1.8 × 104 cm− 1 in the (1 0 0) plane. The
enhancement in the absorption value indicates the electronic contribu­
tion of the methoxy group in system 3 as the methoxy group has an
oxygen atom with two lone pairs that contribute more electrons in
conjugation, thereby increasing the absorption range that assist to excite
the electrons with more energy. Fig. 4 shows that the maximum ab­
sorption value in the (0 0 1) plane was found at a lower wavelength,
whereas remarkable absorption was found in the (1 0 0) plane near the
UV–Visible range for studied systems.
The real and imaginary parts of the conductivity in three planes are
given in Fig. 5. Systems 1 and 2 have equivalent values of real and
imaginary parts. For example, in the (0 0 1) plane, the real part of the
conductivity expressed the highest value 0.9 fs− 1 with an energy of 3.5
eV while the lowest value for the imaginary part was found for these
systems in the (0 0 1) plane. There are some striking differences in sys­
tem 3 that exhibited the real maximum conductivity of 1.2 fs− 1 at 3.5
eV. These components indicate that system 3 has a significantly large
amplitude of conductivity.
3.4. Reflectivity and loss function
A material’s reflectivity links to the coefficient of absorption. The
computed results of reflectivity are shown in Fig. 6. Systems 1 have the
highest reflectivity 0.23 in the plane of (0 0 1) at 4.3 eV and system 2
showed the highest values in the (1 0 0) plane 0.10 at about 3.6 eV.
Whereas system 3 varied significantly. For instance, system 3 has the
highest value of 0.27 of reflectivity at 5 eV in the plane (0 1 0). This
behavior is quite different in the (0 1 0) plane that represents the lowest
Fig. 4. The UV–Vis spectra of the systems 1–3.
4
Computational and Theoretical Chemistry 1203 (2021) 113349
reflectivity while the highest reflectivity values in this plane. Similarly,
this system has the least value of reflectivity for the plane of (1 0 0) with
a maximum value of 0.02 in the range of 2–5 eV.
The energy loss function is also a critical element that indicates the
loss of electron energy when passing through the compound [53]. When
the loss function of entitled systems was compared, a sharp peak was
found that was intense and sharper than the peaks of reflectivity. The
maximum curves are consistent with the rapid decay of reflectivity in
computed loss function graphs. System 1 and 2 have a maximum energy
of loss function at about 3.5, which indicates its energy loss ability
nearly 4.2 eV in the (0 0 1) plane. System 3 showed the same loss
function value at about 4.6 eV with the same intensity in the (0 1 0)
plane. Also, the intermediate value of the loss function was observed in
the (0 0 1) plane. Meanwhile, system 3 showed a comparatively broader
peak area than other systems, as shown in Fig. 7. From the above dis­
cussion, it is observed that the trend of reflectivity and loss function are
quite similar where the concern peaks are linked with three planes.
3.5. Refractive index (n) and extinction coefficient (k)
Refractive index (n) identifies the nature and mobility of electro­
magnetic radiation as it travels through the substrate. The variations
occur when the material reflects incident radiation, indicate its thick­
ness as the refractive index is inversely associated with the material
[54]. The n and extinction coefficient (k) is displayed in Fig. 8. The value
of n varied from a maximum of 1.8 at 3 eV to a lower value of 0.55 that
decreased gradually indicating uniform geometry of systems 1 and 2 in
the (0 0 1) plane. Whereas, in the (1 0 0) plane, intermediate values of n
were found for these two systems (1–2). The same trend of variation was
also observed for the k, where the highest value 1.0 is found at 3.5 eV in
the (0 0 1) plane. However, in system 3, the peaks of n are more intense
R.A. Shehzad et al. Computational and Theoretical Chemistry 1203 (2021) 113349

Fig. 5. The real and imaginary conductivities of the systems 1, 2 and 3.

Fig. 6. The reflectivity of systems 1–3.

Fig. 7. The loss function of systems 1–3.

than systems 1 and 2. There is only 0.02 increment observed in the n
value of (0 0 1) plane at ~3 eV while the values in other planes also
varied such as in the (0 1 0) plane, an intermediate value was observed
and the lowest value of n was obtained in the (1 0 0) plane. The higher
values of n in system 3 reveal that it is a better candidate with maximum
interaction ability as light traveling will be lower in this medium.
Meanwhile, the k value varied exceptionally, where the broader peak
was observed in the range of 3–5 eV at ~1.1 value in the (0 0 1) plane.
System 3 has the lowest value of k in the (1 0 0) plane with a maximum
value of ~0.2 in the range of 2–6 eV.
3.6. Electronic band structures
The electronic band structure is crucial in solid-state materials to
analyze the electronic conduction from the valence band to the con­
duction band as conduction relies on the band gap. The computed en­
ergy gaps of systems 1, 2, and 3 were found 1.821, 1.678, and 1.724 eV,
respectively. From Fig. 9, it can be seen that systems 1 and 2 have an
indirect energy band gap while system 3 has a direct band gap. The band
structure is direct when there is a uniform relation of the band observed
from both the valence band and the conductive band, which is more
critical for photon emission. Simultaneously, the indirect bandgap has

5
R.A. Shehzad et al.
Fig. 8. Refractive index (n) and extinction coefficient (k) of systems 1, 2 and 3.
Fig. 9. The electronic band structures of the entitled systems.
no uniform relation and includes photons and 10honons, making it less
conducive [55,56]. In system 1, the highest zone of valence band max­
ima (VBM) in indirect band structure was found at the Brillouin zones of
G and B, whereas conduction band minima (CBM) found at the Brillouin
zones of A. In system 2, the highest Brillouin zone of VBM was observed
at the G zones, while the lowest CBM was observed near to A zone. When
the band gap of entitled systems was compared, the lowest band gap
(1.678 eV) was found for system 2 that facilitated the smooth conduc­
tion of electrons from VBM to CBM compared to systems 1 and 3. System
3 has a direct band with a bandgap of 1.724 eV. However, systems 1 and
2 have indirect band gaps having 1.821 eV and 1.678 eV band energy
from B to A and G to A zone, respectively.
3.7. The density of states
The total density of state (TDOS) and partial density of state (PDOS)
analysis have been conducted to estimate the contributions of individual
orbitals and to understand the complete electronic distribution for sys­
tems 1–3. The TDOS study demonstrated the cumulative number of
states existing in the system, the carrier’s accumulation, and the charge
distribution in lower orbitals. In system 1, the TDOS highest values were
found near 122 electrons/eV at about − 5 to − 0.1 eV representing the
lower molecular orbitals. From the TDOS, it seems that the s-subshell
contribution is negligible than p-subshell as the maximum number of
states were found at 90 electrons/eV on − 2.3 and − 1.4 eV energies. In
system 2, a sharp peak was observed at − 2.3 eV with the TDOS of 60
electron/eV, whereas negligible contribution was found for s-subshell
because p-subshell and TDOS are precisely the same. Similar to system 1,
system 3 also showed the same highest amplitudes of TDOS and PDOS.
The highest TDOS amplitude of 60 electrons/eV was found at the energy
6
Computational and Theoretical Chemistry 1203 (2021) 113349
of − 2.3 eV, where the highest contributing moiety is the p-subshell.
After the careful analysis of these systems, only the system 1 and 3 have
the maximum amplitude in TDOS and PDOS from s- and p-orbitals that
are higher than the system 2. The calculated spectra of TDOS and PDOS
amplitudes of the entitled system are displayed in Fig. 10.
3.8. Electronic coupling analysis
Overlap elements can be analytically calculated, and, thus, the
interacting matrix element gives conveniently until the proportionality
is assumed. It is true for the direct conversion from donor to acceptor,
but the successful overlap is not simply the donor–acceptor overlap
where bridges interfere, and the scheme would then collapse. Rather
recently, corresponding orbital techniques, based on King et al.[57]
have been used to calculate efficient Hamiltonian elements for non-
orthogonal structures. This is a straightforward approach that can
generate minimal matrix components, is useful for wave functions that
are correct and elaborated (multifiguration), and can include vibronic
effects quickly. On the other hand, the whole mechanism needs com­
plete computation and is complicated for huge structures. In tight-
binding type models, Hopfield et al.[58] have extensively used wave
function analysis to explore the essence of bridge-assisted transfer,
especially in multiple bridges, usually in protein applications [59].
Cluster geometries and electronic couplings of systems 1 and 3 are
shown in Fig. 11, where arrows indicate only potential main paths for
charge transport. System 2 is similar both in geometry and electronic
couplings and thus is not shown here. All the electronic couplings be­
tween molecules in a cluster are in Tables S1–S6. For molecular geom­
etry, in system 1, a pair of monomers constructs one π-stacked dimer
(10–1, 11–2, etc., see Fig. 12) while system 3 shows columns of 1D
R.A. Shehzad et al. Computational and Theoretical Chemistry 1203 (2021) 113349

Fig. 10. The partial and total density of state (PDOS and TDOS) of systems 1, 2 and 3.

Fig. 11. Electronic coupling matrix elements for hole (orange) and electron (black) in the systems 1 (a) and 3 (b). Coupling matrix elements are given in unit of meV.

π-stack structures (4–8–3, 8–12–7, 2–9–1, 6–11–5). Electronic couplings
for hole and electron are examined (Fig. 11). In system 1, the largest
electronic couplings are found for π-stacked pairs, where the electronic
coupling is found for electrons (|Velectron|) = 49.3–55.0 meV and hole |
Vhole| = 43.3–61.6 meV, respectively. These values for the electron and
hole should coincide in a periodic system, respectively, though they are
not in the results because of lack of translational symmetry. On the other
hand, the second-largest electronic couplings for electrons are much
smaller, |Velectron| = 1.6–5.7 meV, compared to the largest ones. The
situation is similar for the electronic hole couplings, which are slightly
larger than those for the electrons, |Velectron| = 1.9–21.2 meV. Hence, the
result indicates that electron charge transport for system 1 is superior to
the hole charge transport and that the transport pathways are like a 2D
conductor. However, the effective electronic couplings are |Velectrons| <
5.7 meV and |Vhole| ≤ 21.1 meV because the charge transport rate is
determined by a transport path’s bottleneck.

Fig. 12. Geometry of molecular clusters of the system 1 (a), 2 (b) and 3 (c).

7
R.A. Shehzad et al.
In system 3, the situation differs significantly from systems 1 and 2.
As found in Fig. 11b, the hole’s electronic couplings are large, |Vhole| =
104–111 meV, and 1D conductive pathways exist. The column–column
electronic couplings are much weaker than these 1D pathways, |Vco­ hole
lumn–column
| ~ 0.5–9.6 meV, about one order smaller than the 1D path­
ways. Similar 1D transport pathways are also found for the electrons in
system 3, though the amplitudes of electronic couplings are much
smaller than those for the holes, |Vhole| = 12.1–26.8 meV. Because the
electronic coupling for holes in system 3 is approximately five times that
of system 1, the electron transport rate of system 3 is expected to be 52 =
25 times of system 1.
Consequently, chalcone derivatives 1–3 considered in this study are
more suitable for electron transport than hole transport. The electronic
couplings that dominate the slowest electron hopping in a potential
conductive path are roughly four to ten times larger for the holes than
for the electrons. The transport pathways in systems 1 and 2 are 2D,
while 1D in system 3. The bottleneck rate for electron transport is ex­
pected to be ~25 times faster for system 3 than the others.
4. Conclusions
Thus, the present study of computational modeling of systems 1, 2,
and 3 was carried out to analyze the effect of different electron donor
groups on their optoelectronic properties at bulk levels. A comparative
analysis of the electro-optical properties of the entitled systems has been
performed at the bulk level. Several important electro-optical parame­
ters are discussed in terms of their dielectric function, absorption, con­
ductivity, reflectivity, loss function, refractive index, electronic band
structures, and density of states. For instance, the maximum values of
their dielectric functions are found to be at 3.2, 1.8, and 3.7 eV exhib­
iting diverse substitutional effects on the molecular structures. Besides
this, system 3 showed the highest value of reflectivity and loss function
along with significant absorption in the visible range. Furthermore,
electronic band structure, the density of state, and electronic coupling
investigation have also assisted that system 3 possesses good electro-
optical properties due to the methoxy group. Finally, the electronic
coupling studies showed that system 3 is a good electron transport
material whose efficiency might be approximately five times that of
system 1, the electron transport rate of system 3 is expected to be 52 = 25
times of system 1 making it a good candidate for electro-optical
applications.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgment
The authors from the King Khalid University extend their apprecia­
tion to the Deanship of Scientific Research at King Khalid University for
funding the work through the general research project (GRP/202/42).
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.comptc.2021.113349.
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