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Synergistic engineering of end-capped acceptor and bridge on arylborane-

arylamine macrocycles to boost the photovoltaic properties of organic solar
cells

Article in Optical Materials · January 2022

DOI: 10.1016/j.optmat.2021.111907

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 Optical Materials 123 (2022) 111907

Contents lists available at ScienceDirect

Optical Materials
journal homepage: www.elsevier.com/locate/optmat

Synergistic engineering of end-capped acceptor and bridge on

arylborane-arylamine macrocycles to boost the photovoltaic properties of
organic solar cells
Alvina Rasool a, Saba Zahid a, Muhammad Ans a, *, Javed Iqbal a, b, **, Muhammad Adnan c,
El-Sayed M. Sherif d, M.S. Al-Buriahi e
a
Department of Chemistry, University of Agriculture, Faisalabad, 38000, Pakistan
b
Punjab Bio-energy Institute, University of Agriculture, Faisalabad, 38000, Pakistan
c
Graduate School of Energy Science and Technology, Chungnam National University, 34134, Daejeon, South Korea
d
Mechanical Engineering Department, College of Engineering, King Saud University, Riyadh, 11423, Saudi Arabia
e
Department of Physics, Sakarya University, Sakarya, Turkey

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

Keywords: A new stream of donor- π -acceptor (D- π -A) type arylborane-arylamine based donor contributors namely (BN1,
Conjugated macrocycles BN2, BN3, BN4, BN5) have been drafted by substituting the terminal 2,4,6-tris-(trifluoromethyl)phenyl groups of
Arylborane reference B4N2-FMes (designated as BNR in the current study) with thiophene followed by W1 (4-(5-methyl­
Arylamine
thiophen-2-yl)benzothiadiazole), W2 (2-(3-methyl-5-methylene-4-oxothiazolidin-2-ylidene)malononitrile), W3
DFT
TD-DFT
(3-methyl-5-methylene-2-thioxothiazolidin-4-one), W4 (2-methylenemalononitrile), W5 (2-cyanoacrylicaidme­
thylester) acceptor moieties respectively. The computational characterization was performed via reliable density
functional theory at B3LYP/6–31G (d,p). The optoelectronic parameters of newly planned molecules have been
cross-checked with the reference (BNR). The newly planned (BN1-BN5) conjugated macrocycles have manifested
outperformed results. Amongst all, BN4 has displayed the lowest band gap (2.07 eV), highest λmax (672 nm) in
dichloromethane (DCM), highest ionization potential (IP) and electron affinity (EA) owing to its functionaliza­
tion with cyano (CN) containing strong electron pulling moieties. Out of all reported molecules, BN1 has
explored the lowest reorganization energy (RE) value for the electron (λ- = 0.00224 eV) and hole (λ+ = 0.00266
eV) demonstrating its augmented charge transition. BN1 is characterized by the highest dipole moment (6.31 D)
in DCM addressing its enhanced solubility. Amongst all, BN4 has explored the highest VOC (1.51 eV) due to its
low-lying HOMO. To sum up, the thiophene bridged end-capped acceptor alteration approach has been proved
persuasive in providing the gateway to devise optimistic photovoltaic materials. All currently planned donor
contributors (BN1-BN5) ought to be targeted to assemble upcoming proficient organic solar cells (OSCs).

1. Introduction
The desire of acquiring a potent, ample, economic, and the envi­
ronmentally friendly power source is expanding as time passes [1].
Energy disaster has been a major concern because of the gigantic up­
surge in its demand [2]. The world’s energy supply by non-sustainable
methods for power is evaporating steadily. Although these power
sources are monetary, they are not practical and convey unfriendly
consequences for the climate [3]. In this manner, inexhaustible well­
springs of energy (hydropower, biomass, and solar cells) are some
elective fuel sources in the present era to get energy on a huge scale [4,
5]. Out of all sustainable energy wellsprings, solar cells are the most
promising possibility to satisfy the expanding energy needs [6]. Solar
devices employing inorganic silicon have recently been suggested as
useful components for manufacturing solar cells. They were harmless
and thermally resistant but owing to their inflexible design, low profi­
ciency, and high cost their applications have been hampered. With the
progression of the inorganic material based solar panels, the electrical
properties of silicon were explicated, and the charge transport features
of silicon were the paramount lead in fostering a solar device. Thus, the

* Corresponding author.
** Corresponding author. Department of Chemistry, University of Agriculture, Faisalabad, 38000, Pakistan.,
E-mail addresses: ansbhatti24@gmail.com (M. Ans), Javed.Iqbal@uaf.edu.pk, javedkhattak79@gmail.com (J. Iqbal).

https://doi.org/10.1016/j.optmat.2021.111907
Received 18 October 2021; Received in revised form 27 November 2021; Accepted 13 December 2021
Available online 18 December 2021
0925-3467/© 2021 Elsevier B.V. All rights reserved.
A. Rasool et al.
solar cell was comprised of silicon as inorganic-based material [7].
Organic photovoltaics (OPVs) have gained the incredible consider­
ation of analysts. They are believed to be more compelling as they
exhibit versatile morphology, flexibility, tunable energy levels, and low-
cost manufacturing [8,9]. The surface morphology of OPVs makes them
more absorptive, and their high purity prompts more prominent pro­
ductivity than inorganic candidates. Over recent many years, 11.7%
expansion has been reported in the working efficiency of fullerene OSCs
[10]. In addition to their high working efficiency, fullerene subordinates
have a few drawbacks, for example, their increased band gap which
leads to feeble absorption range, high orchestrating cost, heat and
photochemical instability [10,11].
To tackle these drawbacks, non-fullerene acceptors have been draf­
ted. Non-fullerene acceptors have adjustable energy levels, a broad ab­
sorption spectrum, minimal expense and a simple strategy for assembly
and sanitization [10,12]. The donor-acceptor structural and optoelec­
tronic properties assume a critical part in deciding the working effi­
ciency of the devices [10].
Molecules accompanied by the donor-π-acceptor (D- π -A) framework
are of grave importance owing to their vast bioimaging and optoelec­
tronic applications [13]. Tricoordinate organoboranes being the strong
electron acceptors are of current interest. Their ability to accept elec­
trons arises from the overlapping of empty pz orbital on boron with the
π-conjugated framework [14]. Thus, the introduction of the tricoordi­
nate organoborane units into the π-conjugated framework is an effective
approach to fine-tune the optoelectronic features. Tricoordinate orga­
noborane groups along with electron-donating moieties like arylamines
results in efficient intramolecular charge transfer (ICT). Conjugated
macrocycles excel all other π-conjugated systems owing to their elegant
structure and promising optoelectronic characteristics. Different
electron-donating and pulling moieties can be substituted into these
cyclic systems to get distinctive properties [15].
In our present report, π-conjugated macrocycle B4N2-FMes has been
taken as a reference molecule designated as BNR. The reference (BNR)
exhibits trigonal planar geometry constituting triarylamine donors
fringed with bis(boryl) fluorene acceptor units and 2,4,6-tris-(trifluoro­
methyl)phenyl groups. We have planned 5 new small-donor molecules
(BN1, BN2, BN3, BN4, BN5) by substituting the terminal 2,4,6-tris-(tri­
fluoromethyl)phenyl groups of model (BNR) with thiophene followed by
Scheme 1. Schematic view of designed chromophores.
2
Optical Materials 123 (2022) 111907
W1 (4-(5-methylthiophen-2-yl)benzothiadiazole), W2 (2-(3-methyl-5-
methylene-4-oxothiazolidin-2-ylidene)malononitrile), W3 (3-methyl-5-
methylene-2-thioxothiazolidin-4-one), W4 (2-methylenemalononitrile),
W5 (2-cyanoacrylicaidmethylester) acceptor groups respectively. All the
5 freshly drafted molecules (BN1, BN2, BN3, BN4, BN5) are the de­
rivatives of the model molecule (BNR). Scheme 1 portrays the D− π− A
configuration of molecules. Fig. 1 displays Chem Draw sketches of
researched molecules. The influence of structural tailoring on BNR and
newly designed (BN1, BN2, BN3, BN4, BN5) molecules have been
thoroughly investigated to acquire insight into their physiochemical
characteristics.
2. Computational details
Density functional theory (DFT) is the most thriving theory to
explore the electronic properties of molecules realistically concerning
quantum mechanical principles [16–19]. In the present quantum me­
chanical report, molecular frameworks were drawn using GaussView 5.0
[20]. All the computational simulations were theoretically assessed with
the assistance of Gaussian 09 programs [21]. To inspect the constancy of
our calculations, initial DFT calculations were performed on the model
molecule (BNR) and the results were cross-checked with the experi­
mental data. Geometric optimization of the model molecule (BNR) was
carried out by employing the four exemplary DFT functionals namely
ωB97XD [22], B3LYP [23], PBEPBE [24]and MPW1PW91 [25] at 6-31G
(d,p). The achieved λmax values of the model molecule (BNR) from four
exemplary functionals were cross-checked with the literature data for
the authorization of the theoretical method. The B3LYP functional was
identified as the best theoretical method because the λmax value dis­
closed by it (395 nm) matches the recorded literature value (407 nm)
[15]. Therefore all the currently devised molecules (BN1-BN5) were
optimized with B3LYP functional at 6-31G (d,p) basis set [26]. The
internationally recognized time-dependent density-functional theory
(TD-DFT) was used to demonstrate the characteristics of the excited
state [27]. Simultaneously, the solvent effect of dichloromethane (DCM)
was modelled by employing IEFPCM (integral equation formation
polarizable continuum model) [28]. The absorption profile was
computed both in the gas and solvent phases. Computational trans­
figuration of λmax values was done by Swizard program [29].
A. Rasool et al. Optical Materials 123 (2022) 111907

Fig. 1. Molecular frameworks of model (BNR) and devised moieties (BN1-BN5).

Collectively λmax values were plotted via Origin 6.0 program [30]. modification during the charge transport, respectively. To model the
FMOs analysis, DOS calculations, TDM examination, reorganization changes in cationic and anionic geometry of reference as well as newly
energy and dipole moment simulations were computationally accom­ devised molecules, the focus is on the λi. The external reorganization
plished by optimal theoretical DFT functional B3LYP/6-31G (d,p). For energy has been neglected in the present investigation. The mobility rate
analyzing the contribution of molecular fragments, DOS files were of the electron (λ-) and hole (λ+) was computed by using equation (2)
pictured via PyMOlyze 1.1 [31]. Estimation of electron densities and and (3) [33].
electronic transitions were executed by using the Multiwfn 3.7 software [ ] [ ]
λ− = E0− − E0 + E−0 − E− (2)
[32].
To model the electron and hole transfer rate equation (1) is the key [ ] [ ]
parameter. Total reorganization energy is the sum of internal (λi) and λ+ = E0+ − E0 + E+
0 − E+ (3)
external reorganization energy (λo) [8].
λ = λi + λo (1) E0+ , E0− = Neutral molecule energy for cation or anion.
E+0 , E0 = Energy of cation or anion from optimized geometry of the
−
Inner-sphere and outer-sphere reorganization energy speak for
neutral molecule.
alteration within the structure of molecules and external environment

3
A. Rasool et al.
E0 , E+ , E− = Single-point energy of the neutral molecule, cation, and
anion from their optimized geometry.
3. Results and discussion
In this current report, firstly the absorption profile of the model
molecule (BNR) was computed via the four DFT functionals (B3LYP,
PBEPBE, MPW1PW91, ωB97XD) in the gaseous and solvent medium as
displayed in Fig. 2.
The λmax of BNR displayed by B3LYP (395 nm) was in close agree­
ment to the recorded literature λmax value (407 nm) [15] as displayed in
Fig. 3 so B3LYP/6-31G (d,p) has been used for all simulations in the
present DFT study.
3.1. Ground state geometric optimization, dihedral angle (θ) and bond
length (L)
Molecular geometry has a remarkable influence on optoelectronic
properties [34,35]. The optimization of the model molecule (BNR) along
with the currently aimed molecules (BN1-BN5) has been carried out by
the optimal selected DFT functional. The optimized framework of all
reported molecules has been displayed in Fig. 4.
The optimized geometry is manifesting that the central donor core
has arrayed itself in one plane with the curvy conformation while the
thiophene bridge along with acceptor units holding the planar confor­
mation have lined up themselves out of the plane to minimize the po­
tential energy surface (PES). In the current initiative, the representative
bond lengths (L) and dihedral angles (θ) as displayed in Fig. 5 have been
examined to explore the influence of newly introduced thiophene
bridged acceptor moieties on the geometrical configuration of
molecules.
Table 1 expresses the summarized values of representative dihedral
angles and bond lengths. The θ values signify the non-planar confor­
mation of the molecule and demonstrates that newly introduced moi­
eties are sterically restricted and there is less possibility of free rotation.
L varies from 1.54 to 1.56 Å approximately equal to C–C bond length
demonstrating the presence of single bond.
3.2. Frontier molecular orbital (FMO) analysis
Frontier molecular orbitals have a substantial influence on the
charge transport, electronic and absorption properties [36,37]. FMO
epitomizes the charge transport and electronic density distribution
pattern [38,39]. Figs. 6 and 7 is the pictorial representation of FMO and
graphical view of energy levels as well as band gap of the model mole­
cule (BNR) along with the currently devised chromophores (BN1-BN5)
respectively.
Fig. 2. Absorption profile of reference (BNR) in solvent (right side) and gas phase (left side).
4
Optical Materials 123 (2022) 111907
Fig. 3. Comparative analysis of calculated and experimental absorption of
reference (BNR) at four different functionals.
The red and green color symbolizes the positive and negative charge
respectively [40]. The donor unit is symbolized by HOMO and the
acceptor is represented by LUMO. HOMO and LUMO electronic density
of the model molecule (BNR) is entirely populated on the donor part
merely. The FMO of all newly devised molecules (BN1-BN5) seems to be
similar. HOMO electronic cloud is primarily diffused on donor moiety
and LUMO electronic cloud is scattered on thiophene bridge and
acceptor units.
In all currently devised molecules, more charge is populated on the
acceptor moieties. More charge concentration on the acceptor units
symbolizes that charge transmission has occurred from donor to
acceptor via thiophene bridge proficiently. The HOMO, LUMO energies,
and band gap (Eg) of the model molecule (BNR) and the devised chro­
mophores (BN1-BN5) have been reported in Table 2. The HOMO en­
ergies of all reported molecules have been explored as BN1(-4.96 eV)>
BNR(-5.23 eV)>BN3(-5.26 eV)>BN5(-5.33 eV)>BN2(-5.49 eV)>BN4
(-5.51 eV). The LUMO energies of model as well as currently devised
molecules has been prospected as BNR(-2.47 eV)>BN1(-2.77 eV)>BN3
(-3.04 eV)>BN5(-3.13 eV)>BN2(-3.36 eV)>BN4(-3.44 eV). The newly
devised chromophores (BN1-BN5) have manifested a smaller Eg value
than model molecule (BNR) owing to strong electron pulling acceptor
substituents’ presence. The incorporation of strong electron pulling
groups in the structure has congested the Eg value of all newly devised
molecules. A smaller band gap paves the way for more easily excited
electrons and thus leads to efficient PCE. The Eg value of all reported
molecules is decreasing as BNR(2.76 eV)>BN3(2.22 eV)>BN5(2.20
A. Rasool et al.
Fig. 4. Optimized frameworks of BNR and BN1-BN5.
eV)>BN1(2.19 eV)>B2(2.13 eV)> BN4(2.07 eV). The Eg value of the
model molecule is higher than all newly devised molecules because it is
devoid of strong acceptor moieties that could shift the electronic density
from HOMO to LUMO. The BN4 has expressed the lowest Eg among all
reported molecules because it is accompanied by Cyano (CN) containing
W4 (2-methylene malononitrile) acceptor substituent leading towards
the propitious charge transfer from occupied to unoccupied molecular
orbitals. CN group tends to improve the molecular electron deficiency by
its hybridized carbon and nitrogen atom and optimizes the electron
accepting nature of the molecule. The reduced Eg value of BN4 is
ascribed for its bathochromic shift.
From the above interpretation of FMO, it is cleared that all currently
devised molecules (BN1-BN5) can be termed as soft molecules owing to
the lower band gap, lower stability, and high chemical reactivity. These
low band gap molecules (BN1-BN5) can provide useful insight to be used
as auspicious charge transferring candidates for OSCs.
5
Optical Materials 123 (2022) 111907
3.3. Ionization potential (IP) and electron affinity (EA)
IP and EA are the distinguishing factors to scrutinize the charge
transmission nature. IP and EA are strongly correlated. Molecules
accompanied by higher EA and lower IP are characterized by efficient
charge transmission. Compounds accompanied by electron-donating
moieties have lower IP because HOMO becomes destabilized and so
the removal of electrons becomes easier. Compounds accompanied by
strong electron-withdrawing substituents manifest high IP value owing
to stabilized HOMO levels. Stabilized energy levels facilitates the elec­
tron abstraction from donor moiety by acceptor unit [10,41]. Table 2
expresses the summarized values of IP and EA of investigated molecules
calculated following equation (4) and (5) respectively.
[ ]
IP = E+ 0 − E0 (4)
[ ]
EA = E0 − E−0 (5)
Among all designed molecules BN1 manifested the lowest IP (5.57
eV) owing to high energy HOMO (-4.96 eV) and lowest EA (2.16 eV)
A. Rasool et al. Optical Materials 123 (2022) 111907

Fig. 5. Computed dihedral angles (θ) and bond lengths (L) of reference (BNR) and BN1-BN5.

3.4. UV–visible spectral analysis

Table 1
Representative dihedral angles (θ in degree) and bond lengths (L in Å) of
Harvesting and absorption of light energy are the central parameters
reference (BNR) and devised moieties (BN1-BN5).
that have gained momentum in photocurrent generation. The UV–vi­
Molecules θ L sible spectra provide an insight into the electronic excitations and
BNR 8.74 1.60 charge transfer analysis, so UV–visible spectra should be evaluated [10,
BN1 19.1 1.54 41,42]. The absorption profile of currently devised molecules
BN2 20.8 1.55
(BN1-BN5) in the gaseous and solvent phase are expressed in Fig. 8.
BN3 20.1 1.55
BN4 19.5 1.56 In the present investigation, the absorption profile has been simu­
BN5 19.3 1.55 lated in both gaseous and solvent (dichloromethane) phases by
employing the TDDFT calculations in the IEFPCM model as the results
have been reported in Tables 3 and 4, respectively.
owing to high energy LUMO (-2.77 eV). BN4 explored the highest IP The absorption profile illustrates that all newly devised molecules
(6.24 eV) due to low energy HOMO (-5.51 eV) and highest EA (2.73 eV), (BN1-BN5) are accompanied by a higher λmax value than the model
credited to its low-lying LUMO (-3.44 eV). The negative inductive effect molecule (BNR). The λmax value is in strong alliance with the band gap. A
of CN in W4 electron pulling moiety is the plausible reason for the lower band gap leads to an enhanced λmax value. That is why all
observed IP and EA values of BN4. All designed molecules have explored currently devised molecules are accompanied by higher λmax values. The
high values of EA due to acceptor modification responsible for efficient absorption profile supports the fact that all devised molecules are
charge transfer. accompanied by strong electron-pulling moieties. The λmax value of all

6
A. Rasool et al.
Fig. 6. FMO portray of reference (BNR) and devised moieties (BN1-BN5)
having 0.02 isosurface value.
currently investigated molecules in dichloromethane solvent is
decreasing as BN4(672 nm)>BN2(640 nm)>BN5(633 nm)>BN3(627
nm)>BN1(602 nm)>BNR(395 nm). Out of all reported molecules, the
highest λmax value has been displayed by BN4 because of its lowest band
gap and cyano containing W4 (2-methylene malononitrile) strong
7
Optical Materials 123 (2022) 111907
electron-pulling moieties. CN group serves as electron capturing moiety
to facilitate the charge transmission from donor to acceptor. CN group
also escalates the molecular conjugation and pushes the absorption to­
wards a longer wavelength by attaching to the conjugated framework of
the molecule. CN group augments the photovoltaic activity of OSCs by
lowering the energy of FMOs.
Another important tool to scrutinize the optical use of the studied
molecules is the light harvesting efficiency (LHE). LHE is computed via f
value and signifies the compound photocurrent response [43].
LHE = 1 − 10− f
(6)
Larger LHE compounds showed large photocurrent responses and
vice versa. LHE of currently reported structures in both gas and solvent
medium has been calculated by equation (6) [43], and the results have
been summarized in Tables 3 and 4. A pronounced shift in LHE values of
newly devised structures has been observed by structural modifications.
Consequently, among all devised structures (BN1-BN5) the highest LHE
value has been displayed by BN1, which is attributed to its augmented
photocurrent generation. Keeping in view the above discussion, all
currently devised structures (BN1-BN5) can be used as propitious aspi­
rants for contriving the future proficient OSCs.
3.5. Quantum chemical parameters
To scrutinize the chemical reactivity and kinetic stability of newly
engineered molecules different chemical parameters have been calcu­
lated and results have been summarized in Table 5.
(EHOMO + ELUMO )
Chemical potential (μ) = (7)
2
Equation (7) [44] has been used for calculating chemical potential.
Chemical potential describes the electronic cloud escaping capability
[45]. The freshly designed molecules (BN1-BN5) are accompanied by
higher values of negative chemical potential indicating that they are
highly reactive as well as stable compounds hence cannot decompose
easily. The designed molecules exhibit a greater value of chemical po­
tential than PC61BM indicating that they have a greater ability to donate
electrons.
(ELUMO − EHOMO )
Chemical hardness (η) = (8)
2
1
Chemical softness (S) = (9)
η
Chemical hardness and softness values calculated by using equations
(8) and (9) [44] respectively, demonstrates that all researched mole­
cules (BN1-BN5) are soft molecules accompanied by the lowest bandg­
aps and enhanced chemical reactivity.
(EHOMO + ELUMO )
Electronegativity (χ ) = − (10)
2
χ2
Electrophilicity index (ω) = (11)
2(η)
Electronegativity and electrophilicity index values have been simu­
lated using equation (10) and (11) [44] respectively. Both are usually
correlated and quantitatively explain the electron-accepting nature of
molecules [45]. All designed molecules (BN1-BN5) have manifested
higher values of electronegativity and electrophilicity index than the
reference (BNR) advocating the fact that newly designed molecules are
accompanied by strong electron-withdrawing moieties. BN1-BN4 are
accompanied by low values of electronegativity and electrophilicity
index as compared to PC61BM indicating that they have less ability to
attract electrons from PC61BM and behave as an electron donor.
μ
Total amount of charge transfer (ΔNmax) = − (12)
η
A. Rasool et al. Optical Materials 123 (2022) 111907

Fig. 7. Graphical representation of computed (a) HOMO LUMO energy levels (b) band gap (Eg) for BNR and BN1-BN5.

The total amount of charge transfer is another parameter to scruti­

Table 2
nize the charge transferring capability of all freshly planned molecules,
Energies of HOMO and LUMO, band gap (Eg), ionization potential (IP), and
calculated by using equation (12) [46]. The summarized results in
electron affinity (EA) of reference (BNR) and devised moieties (BN1-BN5).
Table 5 have shown that all newly engineered molecules (BN1-BN5)
Molecules HOMO (eV) LUMO (eV) Eg (eV) IP (eV) EA (eV) have a greater ability to transfer charge than the reference (BNR).
BNR − 5.23 − 2.47 2.76 6.06 1.52 Keeping in view the above discussion, the freshly designed molecules
BN1 − 4.96 − 2.77 2.19 5.57 2.16 ought to be focused to prepare elite materials for future proficient solar
BN2 5.49 3.36 2.13 6.19 2.72
devices.
− −
BN3 − 5.26 − 3.04 2.22 5.96 2.38
BN4 − 5.51 − 3.44 2.07 6.24 2.73
BN5 − 5.33 − 3.13 2.20 6.07 2.43

Fig. 8. Absorption profile of BNR and newly planned structures (BN1-BN5) in DCM (right side) and gas (left side).

Table 3
Calculated and experimental λmax (nm), interaction coefficient, first transition energy (ΔE), highest oscillator strength (f), light harvesting efficiency (LHE), major
molecular transitions, of the reference (BNR) and devised moieties (BN1-BN5) in gaseous phase (H= HOMO, L = LUMO).
Molecules Calculated λmax (nm) Experimental Interaction Coefficient ΔE (eV) f LHE Major Molecular transitions
λmax (nm)

BNR 391 407 0.69 3.17 0.19 0.35 H→L (69%)

BN1 634 ─ 0.54 1.96 0.24 0.42 H→L (54%)
BN2 615 ─ 0.65 2.02 0.04 0.09 H→L (65%)
BN3 635 ─ 0.65 1.95 0.24 0.42 H→L (65%)
BN4 629 ─ 0.65 1.97 0.03 0.07 H→L (66%)
BN5 604 ─ 0.61 1.94 0.25 0.44 H→L (61%)

8
A. Rasool et al. Optical Materials 123 (2022) 111907

Table 4
Calculated and experimental λmax (nm), interaction coefficient, first transition energy (ΔE), highest oscillator strength (f), light harvesting efficiency (LHE), major
molecular transitions, of the reference (BNR) and devised moieties (BN1-BN5) in dichloromethane (H= HOMO, L = LUMO).
Molecules Calculated λmax (nm) Experimental Interaction Coefficient ΔE (eV) f LHE Major Molecular transitions
λmax (nm)

BNR 395 407 0.69 3.14 0.55 0.72 H→L (69%)

BN1 602 ─ 0.45 2.06 0.47 0.66 H→L (45%)
BN2 640 ─ 0.56 1.94 0.17 0.32 H→L (56%)
BN3 627 ─ 0.10 1.98 0.17 0.32 H→L (100%)
BN4 672 ─ 0.59 1.84 0.17 0.32 H→L (59%)
BN5 633 ─ 0.62 1.96 0.18 0.34 H→L (62%)

analyses. Briefly, the DOS findings have confirmed the FMO results.
Table 5
Chemical potential (μ), chemical hardness (η), chemical softness (S), electro­
negativity (χ ) and electrophilicity index (ω) and total amount of charge transfer
3.7. Molecular electrostatic potential (MEP) surface analysis
(ΔNmax) of reference (BNR) and newly engineered molecules (BN1-BN5).
MEP surface analysis is the propitious tool to appraise the charge
Molecules μ (eV) η (eV) S (eV) χ (eV) ω (eV) ΔNmax (e)
transmission from donor to acceptor moiety in an excited state [41]. In
BNR − 3.85 1.38 0.72 3.85 5.37 2.79 the current study, to figure out the electrophilic and nucleophilic re­
BN1 − 3.87 1.10 0.91 3.87 6.81 3.52 gions, MEP simulations have been carried out at optimal DFT functional.
BN2 4.43 1.07 0.93 4.43 9.17 4.14
−
MEP plots are colored-filled pictures. The red color transcribes the
BN3 − 4.15 1.11 0.90 4.15 7.76 3.74
BN4 − 4.48 1.04 0.96 4.48 9.65 4.31 negative while positive values of electrostatic potential are symbolized
BN5 − 4.89 1.1 0.91 4.89 10.87 4.45 by the blue color. The green color represents the electrically neutral
PC61BM − 4.90 1.20 0.83 4.90 10.00 4.08 region. The red and blue colors exemplify the electrophilic and nucle­
ophilic regions of the molecule, respectively [10].
MEP plot of the model molecule (BNR) explored that the entire
3.6. Density of states (DOS) analysis
molecule is covered by shades of blue representing the positive region
only. MEP plots of studied molecules (BN1-BN5) manifest that the donor
FMO results have been assured via Mulliken charge distribution. The
portion is covered by shades of blue (positive region) and end-capped
DOS analysis expresses the contribution of the molecular fragment in
acceptor moieties are covered by shades of red (negative region) as
raising the bonding (HOMO) and antibonding (LUMO) molecular or­
depicted in Fig. 10.
bitals [47]. DOS calculations also compute the energies of HOMO and
To sum up, based on colonization of electron density in varying re­
LUMO [48,49]. The DOS simulations were computed at the selected DFT
gions, all newly planned molecules being reactive exhibit efficient
functional and transfigured via PyMolyze 1.1.
charge transmission during excitation and can be employed as optimistic
Each fragment’s quantitative contribution in raising the HOMO and
candidates for future proficient solar gadgets.
LUMO is shown in Table 6. The DOS charts for all of the compounds that
have been reported are shown in Fig. 9. FMO and DOS are analogous.
3.8. Transition density matrix (TDM) analysis
The model molecule (BNR) has been divided into two halves, donor and
acceptor units, which are depicted in the plots by green and red lines,
TDM is the most persuasive tool for quantifying the electronic exci­
respectively. The newly developed molecules (BN1-BN5) have been
tation processes (generation, diffusion, recombination, and separation
separated into three parts: donor, bridge, and acceptor, which are rep­
of charges) [50]. TDM demos the quantum geometry of molecules in the
resented by blue, green, and red lines, respectively. In Fig. 9, the donor
excited state. TDM figures out the interrelation between donating and
unit majorly raises the HOMO and LUMO of the model molecule (BNR),
accepting moieties during excitation [12].
whereas the acceptor moieties raise them very slightly. All novel chro­
Using the specified hybrid DFT functional, TDM analysis of BNR and
mophores (BN1-BN5) have essentially identical DOS charts. The donor
the presently targeted (BN1-BN5) molecules was performed. The TDM
contributes the most and the acceptor contributes the least to the
images of BNR and the constructed molecules (BN1-BN5) are shown in
HOMO, whereas the acceptor contributes the most to LUMO and the
Fig. 11. The model molecule (BNR) was split into two parts: donor (D)
donor contributes the least. The thiophene bridge has slightly raised the
and acceptor (A), whereas the constructed molecules (BN1-BN5) were
HOMO and LUMO of the currently devised structures. The band gap
separated into three parts: donor (D), bridge (B), and acceptor (A). The
calculated using DOS plots is identical to that calculated by FMO
baseline and left vertical axes of TDM plots exemplify atoms, whereas
the right vertical scale reflects electron density in the molecule.
Table 6 The involvement of hydrogen atoms has been disregarded due to
Quantitative contribution of molecular fragments in raising the frontier molec­ their little role in the formation of transitions. The charge is more con­
ular orbitals of model (BNR) along with the devised structures (BN1-BN5). stant and confined in the donor part of the model molecule (BNR). The
Molecules Acceptor (eV) Bridge (eV) Donor (eV) charge is more unified on the acceptor section of the newly developed
molecules (BN1-BN5), accompanied by the advantageous diagonal
BNR HOMO 31.6 68.4
(localized electron density) and off-diagonal (charge transfer) features.
─
LUMO 6.4 ─ 93.6
BN1 HOMO 8.9 7.5 83.6 The TDM graphs show good diagonal and off-diagonal charge transfer
LUMO 78.3 12.1 9.6 from donor to acceptor, indicating that electron coupling is weaker in all
BN2 HOMO 1.8 2.6 95.6 currently targeted structures, as evidenced by quicker exciton dissoci­
LUMO 52.6 25.1 22.3
ation, which is required for OSCs construction. The interaction coeffi­
BN3 HOMO 2.1 3.0 94.9
LUMO 50.5 24.8 24.7 cient of the reference molecule (BNR) and the newly devised molecules
BN4 HOMO 1.0 2.1 96.9 (BN1-BN5) is reducing as BNR > BN5>BN4>BN2>BN1>BN3 in DCM as
LUMO 40.8 32.0 27.2 displayed in Table 4. The pictographic view of the interaction coefficient
BN5 HOMO 1.0 2.2 96.8 of researched molecules in DCM has been presented in Fig. 12.
LUMO 37.5 31.3 31.2
The developed moieties have revealed better charge transfer from

9
A. Rasool et al. Optical Materials 123 (2022) 111907

Fig. 9. DOS graphs of BNR and BN1-BN5.

donor fragment to acceptor group via thiophene owing to π-π* pro­ selected DFT functional. Table 7 expresses the ground and excited state
gression as well as the -conjugated framework, based on TDM analysis dipole moment of the model molecule (BNR) along with the newly
and decreased trend of interaction coefficient. So, (BN1-BN5) exhibits devised molecules (BN1-BN5). All the newly devised structures have
marvelous charge dissociation ability as compared to (BNR). manifested the enhanced value of dipole moment in the excited state
(DCM). The pronounced shift in dipole moment advocates the fact that
they have oriented themselves in such a way to lessen the recombination
3.9. Dipole moment (μ)
of charges and to enhance the fill factor (FF) and all freshly drafted
molecules are solution processable molecules. The dipole moment of
Crystallinity and chromophores solubility in organic solvents can be
newly designed structures in DCM lies in the range of 2.37–6.31 D. The
approximated employing the dipole moment (μ) presumption. Highly
highest value of dipole moment has been displayed by BN1 due to its
crystalline materials have a lower probability of possessing anomalous
greater solubility in the DCM and owing to the presence of polar regions
charge transfer states. Higher the μ, noteworthy is the solubility of the
in their structures which facilitates self-assembly, reduces exciton
molecule in organic solvent and higher will be the charge transfer effi­
recombination, and aid in multilayer fabrication. The dipole moment of
ciency. The solvency of the molecules is emphatically related to the
newly designed molecules is decreasing as BN1>BN2>BN4>BN3>BN5
smooth configuration of the donor-acceptor integrated layer in OSCs
in both ground and excited states as presented in Fig. 13.
[51–53]. Smooth morphology of the thin film provides insight for effi­
cient transfer of charge and efficient charge transfer is the remarkable
characteristic of the effectual OSCs [12,54].
In the current report, the dipole moment has been computed via

10
A. Rasool et al.
Fig. 10. The MEP portray of reference (BNR) and devised moieties (BN1-BN5).
3.10. Charge carrier transport properties
Reorganizational energy is the most presumptive parameter to gauge
the charge carrier transport properties [55]. It is characterized as the
energy necessary for the structural adjustment and deformation of the
reactant and its integrated solvent molecules [56]. The external reor­
ganization has been ignored because it is difficult to estimate. In this
current investigation, the focus is on the internal reorganization energy.
It is statistically evaluated by equations (2) and (3).
Reorganization energy is used to assess the charge transfer rela­
tionship between the donor and acceptor units in each molecule. It is
inversely proportional to the rate of charge transfer. The structure of
anion and cation play a crucial role in determining the probability of
electron transfer from donor and hole transfer in acceptor, respectively.
In the present quantum mechanical investigation, the internal reorga­
nization energies have been computed by using selected optimal DFT
functional. Table 8 is the summarized depiction of internal reorganiza­
tion energy values of the model (BNR) and newly devised chromophores
(BN1-BN5). The λ- values of all investigated molecules are decreasing as
BNR>BN5>BN2>BN4>BN3>BN1 (Fig. 14). The newly devised struc­
tures (BN1-BN5) have manifested a higher electron mobility rate than
the model molecule (BNR). The λ+ values of all investigated molecules
are decreasing as BN4>BN5>BNR > BN2>BN3>BN1 (Fig. 14). Among
11
Optical Materials 123 (2022) 111907
all newly devised structures, (BN1-BN3) has displayed an augmented
hole transfer rate than the model molecule (BNR).
Briefly, all the currently engineered structures have displayed
formidable charge transport properties owing to strong electron pulling
moieties presence as compared to the model molecule. The results
demonstrate end-capped acceptor moieties have a great influence on the
internal reorganization energy. Thus, different features of acceptor units
may ameliorate the transfer rate of charge, however, some groups
encourage electron transport as compared to holes. The low reorgani­
zation energies and acceptor unit π− π stacking generally improve the
optoelectronic characteristics. Hence, all these newly structured mole­
cules can be used as an optimistic aspirant for the upcoming effectual
OSCs.
3.11. Device photovoltaic performance
Open circuit voltage (VOC) being the most rationale parameter has
been used for the theoretical evaluation of the OSCs performance. It is
the maximum amount of current when the applied voltage is zero. To
appraise the power conversion efficiency (PCE), the HOMO and LUMO
of donor and acceptor respectively have been taken into consideration
[54]. VOC has been computed by using optimal selected functional. It is
statistically assessed by using equation (13) [57].
A. Rasool et al. Optical Materials 123 (2022) 111907

Fig. 11. TDM plots of BNR and BN1-BN5.

ELUMO of − EHOMO of the solar cell, charge carrier recombination.

(13)
acceptor donor
V OC = − 0.3
e In the present quantum mechanical report, PC61BM has been used as
In the above-mentioned equation (13) e symbolizes the charge of an acceptor. The geometrical optimization of PC61BM has been carried
molecules and 0.3 symbolizes a constant computed from voltage drop. out via selected DFT functional. The HOMO and LUMO energy of
The elements that influence VOC are light intensity, the temperature of PC61BM has been explored as − 6.1 and − 3.7 eV, respectively. The
LUMO of the acceptor and HOMO of the donor molecule is the scale

12
A. Rasool et al. Optical Materials 123 (2022) 111907

Table 8
Reorganization energy of electron (λ-) and hole (λ+) for BNR and BN1-BN5.
Molecules λ- (eV) λ+ (eV)

BNR 0.01476 0.00635

BN1 0.00224 0.00266
BN2 0.00486 0.00586
BN3 0.00459 0.00528
BN4 0.00470 0.00814
BN5 0.00556 0.00758

Fig. 12. The pictographic view of the interaction coefficient of (BNR) and
devised moieties (BN1-BN5) in DCM.

Table 7
Fig. 14. Reorganization energy of electron (λ-) and hole (λ+) for BNR and
Dipole moment (µ) of BNR and BN1-BN5) in ground (µg) and excited state (µe) as
BN1-BN5.
well as their difference (Δµ).
Molecules μg (Debye) μe (Debye) Δμ
matched with the LUMO of PC61BM.
BNR 6.19 7.13 0.94 The VOC value of the model (BNR) has been explored as 1.23 eV. A
BN1 5.13 6.31 1.17 pronounced shift in VOC values has been manifested by tailoring the end-
BN2 3.99 4.90 0.91
capped acceptors of the model molecule (BNR). The VOC values of
BN3 2.16 2.44 0.27
BN4 3.47 4.31 0.84 devised chromophores (BN1-BN5) have been expressed as BN4 (1.51
BN5 2.34 2.37 0.03 eV)>BN2(1.49 eV)>BN5(1.33 eV)>BN3(1.26 eV)> BNR(1.23 eV)>
BN1(0.96 eV). The highest value of VOC has been manifested by BN4 that
is credited for the effective transfer of electrons from HOMO of donor to
LUMO of acceptor. We believe that the BN4:PC61BM aggregate might be
useful as an active layer in OSCs.
Briefly, the newly drafted molecules (BN1-BN5) should be focused to
assemble upcoming proficient OSCs.

4. Conclusion

Nowadays, solar energy has acquired vital significance because of its

Fig. 13. Dipole moment (µ) of BNR and BN1-BN5 in ground (µg) and excited
state (µe) as well as their difference (Δµ).
parameters for computing the highest VOC. The VOC values of BNR and
the newly developed compounds (BN1-BN5) as well as the acceptor
PC61BM, have been shown in Fig. 15. The developed chromophores
functioned as donors in this work, that’s why their HOMO was cross-
bountiful accessibility and cheap assembling cost. To exploit these ad­
vantages, the present research depends on planning the D- π -A type
donor contributors for OSCs by presenting diverse encouraging accep­
tors as the terminal units. In this current initiative, B3LYP is the optimal
DFT functional to explore the optoelectronic properties of newly plan­
ned molecules (BN1, BN2, BN3, BN4, BN5). All computational investi­
gated parameters of newly planned molecules were cross-checked with
the reference (BNR) to select the most elite molecule for OSCs. The
newly planned molecules have displayed formidable results. The newly
devised molecules (BN1-BN5) have explored reduced energy band gap
and broadened optical absorption than the reference (BNR) due to
strong electron pulling moieties. The band gap of devised molecules
ranges from 2.07 to 2.22 eV while the band gap and λmax of reference are
2.76 eV and 395 nm, respectively. All currently devised molecules (BN1-
BN5) can be termed as soft molecules owing to the lower band gap,
lower stability, and high chemical reactivity. All newly planned mole­
cules are enriched with higher dipole moment in DCM than ground state
addressing their good solubility and less charge recombination. The λmax

13
A. Rasool et al.
Fig. 15. Pictorial view VOC of reference (BNR) and devised moieties (BN1-BN5) along with PC61BM.
values of planned chromophores vary from 602 to 672 nm in DCM.
Moreover, the minimal λ- and λ+ values of newly aimed molecules reveal
their higher electron and hole mobility rate, respectively. The TDM
analysis explored that, the bound electron-hole pairs of newly planned
donor contributors could be easily set apart into electrons and holes
owing to their less interaction coefficient. Moreover, all newly planned
molecules when scaled with PC61BM acceptor displayed higher and
comparable VOC values than reference which suggested that these donor
contributors hold a compelling position in achieving escalating opera­
tional efficiency. Momentarily, thiophene spanned end-capped acceptor
alteration strategy has been proved as an enticing route in giving the
guide to plan extremely powerful photovoltaic materials. So, all newly
aimed structures (BN1-BN5) have the ability to improve the device’s
operating aptness and may be used as primary donor materials in the
development of future adept OSCs.
CRediT authorship contribution statement
Alvina Rasool: Major Contribution, the acquisition, drafting, anal­
ysis, writing original paper, working and interpretation of data, Funding
acquisition, Writing – original draft, Formal analysis. Saba Zahid: The
acquisition, drafting, analysis, working and interpretation of data,
Funding acquisition, Writing – original draft, Formal analysis.
Muhammad Ans: Substantial contribution to research design, the
acquisition, analysis and interpretation of data, and approval of the
submitted and final version, Funding acquisition, Formal analysis.
Javed Iqbal: Substantial contribution to research design, the acquisi­
tion, analysis and interpretation of data, and approval of the submitted
and final version, Funding acquisition, Formal analysis. Muhammad
Adnan: Funding acquisition, Writing – original draft, Formal analysis,
The acquisition, drafting, analysis, working and interpretation of data.
El-Sayed M. Sherif: The acquisition, drafting, analysis, working and
interpretation of data, Funding acquisition, Writing – original draft,
Formal analysis. M.S. Al-Buriahi: The acquisition, drafting, analysis,
working and interpretation of data, Funding acquisition, Writing –
original draft, Formal analysis.
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.
Acknowledgement
The authors concede the technical and financial assistance from
Punjab Bio-energy Institute (PBI), University of Agriculture, Faisalabad
(UAF), Pakistan. We also thank Dr. Khurshid Ayub, COMSATS Univer­
sity Islamabad, Pakistan for additional resources. Researchers Support­
ing Project Number (RSP-2021/33), King Saud University, Riyadh,
14
Optical Materials 123 (2022) 111907
Saudi Arabia.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.optmat.2021.111907.
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