Journal of Molecular Liquids 341 (2021) 117406

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Journal of Molecular Liquids

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

Quantum mechanical/molecular mechanical approach for the simulation

of UV–Vis absorption spectra of p-conjugated oligomers
Md Al Mamunur Rashid a,1, Kyusang Ahn b,c,1, Jonggu Jeon b,c, Minhaeng Cho b,c, BongSoo Kim d,⇑,
Kyung-Koo Lee e,⇑, Kyungwon Kwak b,c,⇑
a
Department of Smart Cities, Chung-Ang University, Seoul 06974, Republic of Korea
b
Center for Molecular Spectroscopy and Dynamics, Institute for Basic Science (IBS), Seoul 02841, Republic of Korea
c
Department of Chemistry, Korea University, Seoul 02841, Republic of Korea
d
Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST), 50 UNIST-gil, Ulsan 44919, Republic of Korea
e
Department of Chemistry, Kunsan National University, Gunsan 54150, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: It is crucial to understand the light absorption features and electronic structures of conjugated organic
Received 13 May 2021 materials for their optoelectronic applications. However, neither reliable interpretations of reported
Revised 23 July 2021 ultraviolet–visible (UV–vis) absorption spectra nor correct predictions of new organic materials have
Accepted 26 August 2021
been made because of the absence of proper calculation methods. To date, excited-state quantum chem-
Available online 28 August 2021
ical calculations, such as configuration interaction singles (CIS) and time-dependent density functional
theory (TDDFT), have provided such information by overlooking the facts that many conformational iso-
Keywords:
mers of conjugated organic molecules can exist at a given temperature and the resulting distributions of
Organic photovoltaic cells
p-conjugated molecules backbone structure can modulate p-conjugated electronic structures. In this study, we introduced a
QM/MM MD simulation computational method combining the quantum mechanical/molecular mechanical molecular dynamics
Molecular conformations simulation (QM/MM MD) and the excited-state electronic structure calculation to include various con-
UV–vis absorption spectrum formers distributed due to the finite temperature and present a near-perfect simulation of experimen-
tally obtained UV–vis absorption spectra. The simulated UV–vis spectrum of 3,6-bis(5-(benzofuran-2-
yl)thiophen-2-yl)-2,5-bis(2-ethylhexyl)pyrrolo[3,4-c]pyrrole-1,4-dione [DPP(TBFu)2], a p-conjugated
organic material for organic photovoltaic cells (OPV), shows excellent agreement with its experimental
spectrum, and each absorption band is assigned to the different conformers with characteristic excitation
energies. We believe that our new method provides an improved interpretation of the electronic struc-
tures as well as the conformational variations of p-conjugated organic materials under ambient
environments.
Ó 2021 Elsevier B.V. All rights reserved.

1. Introduction

Conjugated organic molecules and polymers are essential for

Abbreviations: PES, potential energy surface; DPP(TBFu)2, 3,6-bis(5-(benzo
furan-2-yl)thiophen-2-yl)-2,5-bis(2-ethylhexyl)pyrrolo[3,4-c]pyrrole-1,4-dione;
PCE, power conversion efficiency; PDOS, partial density of states; TDOS, total
density of states; REBG, rotational energy barrier gap; AM1, Austin model 1; PM3,
parameterized model 3; C-PCM, conductor-like polarized continuum model; TP-
BFU, thiophene-benzofuran; TP-DPP, thiophene-diketopyrrolopyrrole; B3LYP, Becke
3-parameter Lee–Yang–Parr; RMSD, root mean square deviation; FMO, frontier
molecular orbitals; FWHM, full width at half maximum; EBE, exciton binding
energy; LHE, light harvesting efficiency.
⇑ Corresponding authors at: Center for Molecular Spectroscopy and Dynamics,
Institute for Basic Science (IBS), Seoul 02841, Republic of Korea (K. Kwak).
E-mail addresses: bongsoo@unist.ac.kr (B. Kim), kklee@kunsan.ac.kr (K.-K. Lee),
kkwak@korea.ac.kr (K. Kwak).
1
The authors contributed equally to this work.
organic electronics, such as organic photovoltaics (OPVs), organic
transistors, organic light-emitting diodes, and organic photodiodes
[1–7]. The electronic and optical properties of p-conjugated
organic materials originate from the structure of their molecular
orbitals, particularly the highest occupied molecular orbital and
lowest unoccupied molecular orbital (HOMO/LUMO) levels, which
are governed by the chemical structure and p-conjugation
strength. For instance, the solar energy conversion process in
OPV devices starts from the light absorption in the photoactive
layer composed of p-conjugated organic materials. The energy of
absorbed light correlates with the electronic structure of the con-

https://doi.org/10.1016/j.molliq.2021.117406
0167-7322/Ó 2021 Elsevier B.V. All rights reserved.
Md Al Mamunur Rashid, K. Ahn, J. Jeon et al.
stituent p-conjugated molecules. Moreover, the detailed light
absorption features are largely affected also by the molecular
structure along the p-conjugated backbone. The molecular confor-
mation of the conjugate backbone is tightly associated with the
spatial extension of p-conjugation and molecular packing or aggre-
gation, which influences the electronic structures. Therefore, con-
siderable experimental and computational approaches have been
devoted to studying the molecular structure–absorption property
relationship of known or newly developed conjugated materials.
[8–10]
A reliable analysis of the ultraviolet–visible (UV–vis) absorption
spectra is important for obtaining detailed electronic and struc-
tural characteristics of the p-conjugated molecular structures. This
information is essential to elucidate the dependence of the photo-
voltaic properties of OPVs on the molecular backbone geometry
and electronic structure. Thus, the accurate and reliable modeling
of the absorption spectra can be an important tool for inferring
experiments, classifying molecular species, demonstrating the
change of electronic and molecular structures in different environ-
ments, and predicting photochemistry. To analyze the UV–vis
absorption feature, various factors should be considered, including
the energies and intensities of electronic transitions (maximum
absorption wavelength and strength), and the finite lifetime of
the excited state and distributed structures (absorption line
shape).
To understand UV–vis light absorption at the molecular level in
terms of the relevant electronic structure, excited-state calcula-
tions, such as configuration interaction singles (CIS) and time-
dependent density functional theory (TDDFT) are required. In most
cases, excited-state calculations have been conducted based on a
single conformation determined by the geometry optimization at
the ground state [11–13]; however, the comparison of the single
excitation energy with the experimental maximum absorption
wavelength (kmax) can be problematic because many factors that
contribute to the spectral shape and kmax value, including temper-
ature effects, are omitted from the theoretical model [13]. A zero-
temperature optimized geometry with the highly planar backbone
of a calculated conjugated molecule has been typically assumed as
the representative structure of the energy minima due to the sta-
bilizing effect of extended p-conjugation. However, there must
be a structural distribution of a given conjugated molecule at a
finite temperature because the potential energy surface (PES) con-
tains many shallow local minima, and this structural distribution
should be deliberately considered to correctly interpret the exper-
imental results. For example, various p-conjugated conformers
with different planarity modulate the effective conjugation length
and produce a distribution of electronic structures and transition
frequencies. The simulated UV–vis spectrum considering con-
former mixtures reflect the finite temperate effect and may exhibit
asymmetric peaks or shoulders which cannot be reproduced only
with quantum calculation based on a single optimized structure.
2. Materials and methods
We introduce a computational method to obtain the UV–vis
absorption spectra of conjugated organic molecules with confor-
mational manifolds at a given temperature, presenting multiple
bands with asymmetric line shapes. In this method, the important
conformers of a conjugated organic molecule were sampled by
molecular dynamics (MD) simulations with quantum mechanics/-
molecular mechanics (QM/MM) potential. Afterward, excited-state
electronic structure calculations were carried out for the set of pre-
dominant conformers, and their excitation energies and oscillator
strengths were combined with the appropriate weight determined
2
Journal of Molecular Liquids 341 (2021) 117406
from the MD sampling, which yielded the simulated UV–vis
absorption spectrum reproducing the details of experimental one.
As isolated oligomers are typically used to model the electronic
properties of OPV materials by ab initio methods [14], we validated
our approach using 3,6-bis(5-(benzofuran-2-yl)thiophen-2-yl)-2,5
-bis(2-ethylhexyl)pyrrolo[3,4-c]pyrrole-1,4-dione [DPP(TBFu)2] as
an example, which consists of diketopyrropyrrole (DPP), thiophene
(TP), and benzofuran (BFU) moieties, as shown in Scheme 1(b). DPP
(TBFu)2 is an efficient donor molecule developed by Nguyen et al.
[15] for OPV applications, with a power conversion efficiency
(PCE) of up to 4.4% and an open-circuit voltage of 0.9 V when
paired with a fullerene derivative acceptor in an OPV device. DPP
(TBFu)2 was purchased from the Merck and was used without fur-
ther purification. The UV–vis absorption spectrum was measured
in the solution of CHCl3 using a Shimadzu UV-2401 diode array
spectrophotometer. The UV–vis absorption spectrum of DPP
(TBFu)2 in solution exhibits a major doublet band in the range of
550–650 nm with two small peaks at 420 and 350 nm. In the pure
solid or mixed states with a fullerene derivative acceptor or in TiO2,
the absorption at 600 nm increased to varying degrees; however,
the overall band structure was maintained in the range of 300–
700 nm [15–17]. It indicates that the intermolecular p-p interac-
tions affects little the absorption feature and the intramolecular
properties mainly determines the asymmetric and complex
absorption spectrum of DPP(TBFu)2. Thus, we focused on the sim-
ulation of the solution-state DPP(TBFu)2 using QM/MM MD and
excited-state electronic structure calculations to investigate the
origins of the experimentally observed absorption bands.
MD simulations with a semiempirical potential, such as Austin
Model 1 (AM1) and Parameterized Model 3 (PM3), are known to
underestimate the activation energy for the rotation of a single
bond between conjugated building units [18,19], potentially lead-
ing to inaccurate rigidity or planarity of the conjugated systems. In
contrast, full QM calculations with ab initio or DFT methods can
provide satisfactory results for conjugated systems of small mole-
cules, although the QM/MM MD simulation is impractical because
of its high computational costs. To simulate the structure of conju-
gated molecules, we calculated the rotational energy barrier gap
(REBG) between the DFT and AM1 methods, as shown in Scheme 1
(a), and applied this difference to the AM1 potential in the MD
simulation.
3. Results and discussions
To investigate the energetics of internal rotation in DPP(TBFu)2,
first, we calculated the potential energy surfaces (PESs) with
respect to the two types of single-bond rotations, as shown in
Scheme 1(b), using truncated thiophene–benzofuran (TP–BFU)
and thiophene–diketopyrrolopyrrole (TP–DPP) units. The 2-
ethylhexyl group on the DPP moiety was replaced by the methyl
group to facilitate the PES calculation. The dihedral angles between
O–C–C–S for the TP–BFU unit and S–C–C–N for the TP–DPP unit
were denoted as u1 (u1 ) and u2 (u2 ), respectively. Using the DFT
0 0
method with the B3LYP functional and the 6-311G (d, p) basis
set, the PES was generated using the scan coordinate method
implemented in the Gaussian 16 package [20]. An implicit solva-
tion model based on the conductor-like polarized continuum
model (C-PCM) was used to include the solvation effect of chloro-
form. Here, the dihedral angle between each unit was scanned with
a step size of 10°, and the geometry was optimized at each angle.
Fig. 1(a) shows that there is almost no energy difference between
the E and Z forms of the TP–BFU unit. Thus, these two conforma-
tions should be considered as initial structures with equal weight
in the MD simulation because the calculated rotational barrier of
~4.5 kcal/mol would not allow easy transition between them. Con-
Md Al Mamunur Rashid, K. Ahn, J. Jeon et al.
Scheme 1. (a) Rotational energy barrier gap (REBG), as the difference between the
potential energy surfaces (PESs) obtained from the density functional theory (DFT)
and Austin Model 1 (AM1) methods. (b) DPP(TBFu)2 molecular structure showing
the two types of single-bond rotation for which REBG is calculated: (i) one between
the thiophene (TP) and benzofuran (BFU) units (u1 and u1 ), and (ii) the other
0
between the TP and diketopyrrolopyrrole (DPP) units (u2 and u2 ).
0
Fig. 1. Rotational energy profile at the B3LYP/6-311G (d, p) level of the (a) TP–BFU and (b) TP–DPP units. (c) Three energetically favorable conformations of DPP(TBFu)2 and
their Boltzmann factors determined from DFT calculations at the B3LYP/6-311G (d, p) level for the ground state.
3
Journal of Molecular Liquids 341 (2021) 117406
versely, the internal steric hindrance between the methyl group on
the DPP moiety and the hydrogen atom on the TP moiety makes
the E form of the TP–DPP unit less stable than the Z form by
1.5 kcal/mol, as presented in Fig. 1(b). Based on the calculated
energy difference, the population of the Z form was predicted to
be more than eight times larger than that of the E form at room
temperature. Thus, it is reasonable to consider only the Z form
for the TP–DPP unit.
Based on the calculated PES, we identified three conformers of
DPP(TBFu)2, which are expected to have the largest populations
in solution. They exhibited the common Z-Z conformations of the
two TP–DPP units and adopted the E-E, E-Z, and Z-Z conformations
of the two TP–BFU units, as shown in Fig. 1(c). Hereinafter, these
three conformers of DPP(TBFu)2 are referred to as E-E, E-Z, and Z-
Z, depending on the conformations of the TP–BFU units. In addi-
tion, quantum calculations for the original DPP(TBFu)2 of all con-
formers with a planar structure were conducted to determine the
relative molecular energy, including energetically forbidden struc-
tures with the E form of TP-DPP unit. As expected, the molecules
with the E conformation of the TP–DPP unit possesses a higher
energy than those with the Z conformation of the TP-DPP unit.
Thus, it is reasonable to consider the conformers with E-E, E-Z
and Z-Z of TP-BFU unit and Z-Z conformer of TP-DPP as the repre-
sentative structure of DPP(TBFu)2 in solution. Unlike the PES calcu-
lation for the truncated TP–BFU units, there exists a difference in
the energies of the E-E, E-Z, and Z-Z forms, which may have origi-
nated from the structural change due to the steric hindrance
between the backbone and the bulky side chain. The obtained
energy difference was converted to the Boltzmann factor, which
will be discussed later.
Md Al Mamunur Rashid, K. Ahn, J. Jeon et al.
To obtain the REBG between the DFT and AM1 methods, we
repeated the same rotational PES calculations for the truncated
TP–BFU and TP–DPP units at the AM1 level. As described in
Figs. S1–S3, the REBG was obtained by the difference in the PESs
from the two methods and modeled by a quadratic function of
the dihedral angles. By applying this DFT-based correction to the
potential energy in the AM1/MM MD simulation, we could
describe the DPP(TBFu)2 backbone structure more accurately than
the AM1 method. This approach provides the advantage of compu-
tational time saving and increased accuracy, simultaneously. All
the MD simulations with the AM1 method were performed by
applying the obtained REBG using the Amber 17 program [21]. It
should also be mentioned that the PES at the AM1 level in
Figs. S1–S3 was obtained with the AM1 method implemented in
Amber. This ensures that the REBG is consistently applied in the
MD simulation based on the implementation of the AM1 method
in Amber [22]. The details of the MD simulations are described in
Supporting Information.
Histograms showing population distributions along the dihe-
dral angle are presented in Fig. 2 for the E-Z form and Figs. S4
and S5 (Supporting Information) for the E-E and Z-Z forms, respec-
tively. The dihedral angle distributions of the two TP–BFU units,
u1 andu1 , are close to the Gaussian function (bell-shaped curve),
0
and the population distribution of the two TP–DPP units, u2 and
u02 , for the E-Z and Z-Z forms show two superimposed normal dis-
tributions (Mshaped curve). This is because the ethylhexyl alkyl
chain on the DPP unit prevents the thiophene unit from forming
a conjugated planar geometry with the DPP unit due to steric hin-
drance. For this reason, the relative populations of the TP–DPP unit
whose u2 (u2 ) is near zero degrees are relatively small for E-E and
0 around 425 nm originated from the S3–S4 excited states, whereas
Z-Z conformers.
To perform excited-state quantum chemistry calculations, a set
of representative structures for each conformer (E-E, E-Z, and Z-Z)
of DPP(TBFu)2 was selected from the MD trajectories using the
ensemble cluster method, where the structural samples from MD
simulations were classified into different clusters based on the root
mean square deviation (RMSD) of atomic positions as imple-
mented in the UCSF Chimera program [23,24]. A representative
geometry was identified for each cluster whose population is dis-
played in decreasing order in Fig. 3 for the E-Z form and in
Figs. S6 and S7 for the E-E and Z-Z forms, respectively. Ten repre-
sentative structures of each conformer were selected and used as
the initial structures for the excited-state calculations. TDDFT cal-
culations with the B3LYP functional and the 6-311G (d, p) basis set
were conducted to obtain the absorption spectrum of the selected
representative structures, using the PCM to introduce the solvation
effect (chloroform, e = 4.7).
The oscillator strengths of 30 representative structures (10
structures from each conformer) of the Z-Z, E-Z, and E-E conform-
ers are displayed in Fig. S8. To consider the relative contribution of
each structure to the ensemble-averaged absorption spectrum, the
oscillator strength from the TDDFT calculation was scaled by the
relative population at the given temperature using the following
equation:
f scaled ¼ F 1 F 2 f TDDFT
Here, fTDDFT is the calculated oscillator strength, F1 is the ratio of
the cluster size of a structure to the total cluster size of represen-
tative structures, and F2 is the Boltzmann factor of each conformer
(E-E, E-Z, or Z-Z), which is determined by the energy of each con-
former in the ground state, as expressed in Eq. (2):
expðbEx Þ
F 2;x ¼ P ðx ¼ E  E; E  Z; Z  ZÞ
x¼EE;EZ;ZZ expðbEx Þ
Journal of Molecular Liquids 341 (2021) 117406
where b ¼ 1=ðkB TÞ with the Boltzmann constant (kB ) and the abso-
lute temperature (T), and Ex is the calculated energy of each con-
former. The F2 values of the three conformers determined from
this calculation are shown in Fig. 1(c). To confirm the contribution
from less-frequently observed structures, we also displayed the
oscillator strengths of 45 structures (15 from each conformer) and
60 structures (20 from each conformer) in Figs. S9 and S10, respec-
tively. Figs. S8–S10 show that the overall spectral features are sim-
ilar regardless of the number of structures considered. Therefore, 30
structures (10 for each conformer) can be used to accurately predict
the UV–vis absorption spectrum.
In Fig. 4(a), we present the experimental UV–vis absorption
spectrum (red line) in solution [14] and the simulated UV–vis
absorption spectrum (black line) of DPP(TBFu)2 in chloroform.
The simulated spectrum was plotted by convoluting the oscillator
strengths of 30 representative structures of the three conformers
(from Fig. S8) using a Gaussian function with a bandwidth of
0.038 eV. To cover almost all the UV–vis regions, we performed
TDDFT calculations up to the 10th lowest singlet excitation (S10)
for all 30 representative structures. Fig. 4(a) clearly shows that
the simulated spectrum successfully reproduces the main features
of the experimental UV–vis absorption spectrum. In particular, the
main peak positions and asymmetric line shapes at approximately
350, 425, and 600 nm obtained from our simulation show good
agreement with those of the experimental spectrum. The simu-
lated absorption spectrum shows the dual main peaks around
600 nm, which originated from the electronic transition from the
ground state to the 1st excited electronic state in different con-
formers. It was also observed that the broad and asymmetric peak
the peak around 350 nm was due to the higher (S8–S10) excited
electronic states. It is evident from the simulated absorption spec-
trum that the asymmetric line shapes and main peaks with high
intensities can be obtained from the distribution of the p-
conjugated structures of the three conformers, which cannot be
obtained the TDDFT calculation of a single structure.
The simulated spectrum is the sum of spectra from 30 represen-
tative structures which include 10 representative structures of
each conformer. To find out the origin of the peaks of the simulated
spectrum of DPP(TBFu)2, we also plotted the UV–vis absorption
spectrum of E-E, E-Z, and Z-Z conformers in Fig. 4(b). The dual
peaks at around 600 nm (636 nm and 590 nm) and 350 nm
(333 nm and 350 nm) come mainly from the E-Z conformer, while
Z-Z conformer has minor contribution on those peaks. The peak at
536 nm represents the E-Z conformer. Two small and broad peaks
at around 425 nm (422 nm and 440 nm) also mainly originate from
the E-Z conformer. Thus, the simulated absorption spectrum of DPP
(TBFu)2 is mainly represented by the E-Z conformer due to its lar-
gest Boltzmann factor as shown in Fig. 1.
In Fig. S11, the iso-surfaces of selected frontier molecular orbi-
tals (FMO) (from HOMO-2 to LUMO + 2) of the most highly popu-
lated structure of the E-Z form are presented. The HOMOs and
LUMOs are mainly contributed by the backbone atoms, while there
is no contribution from the attached side chain. The theoretical
results indicate that the electronic transition that governs the opti-
ð1Þ cal properties of the target molecule is mainly determined by the
structure of the backbone [25,26]. However, it should be noted that
the bulky side chain can induce a conformational change in the
backbone, resulting in a change in the molecular orbital energies.
To investigate the energy of the molecular orbitals with respect
to the structures with slightly different planarity, the HOMO/LUMO
molecular orbital energies of the 30 representative structures of
DPP(TBFu)2 are shown in Fig. 5. In addition, the main transition
ð2Þ
and its contribution to the excited state of the most highly popu-
lated structure of the E-Z, E-E, and Z-Z conformers, including their
HOMO/LUMO energies, are tabulated in Table S1. The contribution
4
Md Al Mamunur Rashid, K. Ahn, J. Jeon et al.
Fig. 2. Population histograms of the four dihedral angles (u1 , u1 , u2 ,u2 ) for the E-Z conformer from the MD simulation.
Fig. 3. Population histograms of the representative structures of the E-Z conformer
in decreasing order as determined by the ensemble cluster method. Each bar stands
for a single cluster or the corresponding representative structure, and the
percentage values are the accumulated population up to 10, 15, and 20 most
frequently observed structures.
of the main transition to the excited state differs depending on the
type of conformer, which might be the origin of the diverse excita-
tion energies and oscillator strengths. The most populated struc-
tures of the E-Z, E-E, and Z-Z conformers indicate that the
conformational change did not significantly affect the FMO ener-
gies. Although the structures of the three conformers possess
almost similar HOMO/LUMO energies, ~ 5.14 eV/~ 3.06 eV,
and HOMO/LUMO energy gaps, ~2.09 eV (see Table S1), Fig. 5
clearly shows that slightly different structures produce a wide
range of HOMO/LUMO energies. At room temperature, the p-
conjugated oligomers in the solution phase exhibit diverse struc-
tures due to thermal motion. Moreover, all the oligomers in the
film state, which are usually prepared by the spin coating method,
accompanied by the rapid vaporization of the solvent or swift cool-
5
Journal of Molecular Liquids 341 (2021) 117406
0 0
ing down [27], do not achieve the most stable geometry. However,
one selected structure that might be the globally optimized struc-
ture has been used to reveal the underlying optoelectronics by
quantum chemistry in general, which leads to a mismatch between
experimentally measured and theoretically estimated HOMO/
LUMO energies. The calculation method tends to underestimate
the energies compared to the experimental results [28]. This might
originate from the cyclic voltammogram (CV) method widely used
to measure the HOMO/LUMO energy level because the HOMO
(LUMO) level can be determined by the species with the worst
oxidative (reductive) stability. In other words, the experimental
HOMO (LUMO) level measured from molecules with different con-
formational structures will increase (decrease) relative to those
estimated from a molecule with a most stable conformational
structure. In addition, the inaccuracy may be due to the intrinsic
limit of quantum calculations.
The suitable electronic structure of the materials is crucial for
determining the fundamental photophysical features of OPVs. To
understand the electronic structure of all the conformers, the total
density of states (TDOS) of the orbitals and partial density of states
(PDOS), which is based on the s-, p-, and d-orbitals (Fig. 6) of the
most probable structure of all three conformers were analyzed
using the Multiwfn software package [29], within a certain range
of energy that covers all the nearby FMOs. The DOS was deter-
mined by convoluting the molecular orbital data with Gaussian
curves and a full width at half maximum (FWHM) of 0.25 eV.
The DOS plot shows the orbital population and validates a simple
assessment of the character of the molecular orbitals. In all the
conformers, it is observed that the d-orbital shows negligible
PDOS (Fig. 6). However, the PDOSs of the s- and p-orbitals domi-
nate the TDOS of the unoccupied orbitals (LUMO, LUMO + 1,
LUMO + 2, etc.), whereas the p-orbitals are the main
contributors to the TDOS of the occupied orbitals (HOMO,
HOMO-1, HOMO-2, etc.).
Md Al Mamunur Rashid, K. Ahn, J. Jeon et al.
Fig. 4. (a) Experimental UV–vis absorption spectrum (red line) and simulated UV–
vis absorption spectrum (black line) at the B3LYP/6-311G (d, p) level of 30
representative structures taken from the MD simulation. Spectral lines were
broadened using a Gaussian function with a width of 0.038 eV. (b) Simulated UV–
vis absorption spectrum (red line) was decomposed into the contribution of each
conformers. (For interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.)
Fig. 5. Distribution of the frontier molecular orbital (FMO) energy levels (HOMO/
LUMO) of each 10 representative structures of three cis-trans conformers.
Several electronic and optical properties, chemical reactivity
parameters, and certain crucial factors that affect the short-
circuit current density (JSC) and open-circuit voltage (VOC), such
as the electron injection driving force (DGinject), light-harvesting
6
Journal of Molecular Liquids 341 (2021) 117406
Fig. 6. Total density of states (TDOS) and Partial density of states (PDOS) of the
most probable structures of the E-E, E-Z, and Z-Z conformers based on the s, p, and d
orbitals.
efficiency (LHE), regeneration energy (DGregen), coupling constant
(|VRP|), exciton binding energy (EBE), oxidation potential at excited
state (E*) and excited-state lifetime (s), have also been investi-
gated. The theoretical background of these properties can be found
in Electronic Supporting Information. The DGinject, E*, LHE, DGregen,
of the 10 representative structures of each of the E-E, E-Z, and Z-Z
conformers are plotted in Fig. S12. The DGinject values of all the con-
formers are distributed roughly from 0.45 to 0.95 eV. The E-E
conformer show higher negative DGinject values comparing to E-Z
and Z-Z conformers ensuring that the former will exhibit fast elec-
tron injection, which eventually influences the JSC. A wide range of
DGinject indicates that the driving force for electron injection can be
changed depending on the structural changes of the representative
geometries of the conformers. Moreover, a high LHE increases the
Md Al Mamunur Rashid, K. Ahn, J. Jeon et al.
light-capturing ability and improves the efficiency of the OPV by
increasing the JSC. Evidently, the LHEs are distributed between
0.89 and 0.98, which implies that the LHE is affected by not only
the conformational change but also the structural change of the
same conformer. The representative structures of the E-Z and Z-Z
conformers show higher LHE values (0.96 ~ 0.99) than those of
the E-E conformers (0.89 ~ 0.97), indicating that the former will
enhance the JSC more than the latter. The DGregen values of the rep-
resentative structures of the three conformers show that the DGre-
gen values are not widely distributed for each of the representative
conformers, although their population ranges from 1.05 to 1.14 eV
based on different types of conformers. The eVOC, EBE, |VRP|, and s
values of the 10 representative structures of each of the E-E, E-Z,
and Z-Z conformers are plotted in Fig. S13. The overall eVOC values
expanded from 0.63 to 0.69 for all the conformations of DPP
(TBFu)2. The E-E conformers show a low eVOC, whereas the E-Z
and Z-Z conformers show high eVOC values, indicating that the lat-
ter structures are more favorable for achieving a high VOC. A wide
range of EBE and s values are displayed for the various conformers,
which shows that the EBE range and s vary based on various con-
formational structures. The E-E conformers show a wide range of
EBE and s values compared to the E-Z and Z-Z conformers. The
reorganization energies of the most probable structures of the
three conformers were calculated, and the results are presented
in Table S2. The total reorganization energy, ki (summation of kh+
and ke-), is the highest for the E-E conformer, while ki is the lowest
for the Z-Z conformer, indicating that the Z-Z conformer will exhi-
bit faster electron transfer and higher JSC than the E-E confirmer,
consequently affording better PCE. Based on the above observa-
tions, we, therefore, recommend that a number of representative
structures from the various stable conformers of a molecule should
be considered in analyzing the experimental data, as their several
photophysical properties vary over a wide range, which can affect
the efficiency of the OPV cell.
4. Conclusion
In this study, we introduced a method to calculate the complex
and broad UV–vis absorption spectrum of conjugated molecules
with high accuracy using a combination of the QM/MM MD simu-
lation and the excited-state electronic structure calculations. Clas-
sical MD simulations does not correctly describe the rigidity of
conjugated systems and allow rotation along a single bond
between conjugated building blocks with a small activation energy
at room temperature. To overcome this problem, we initially chal-
lenged the MD simulation with a semiempirical quantum method,
the AM1 potential. However, even though the semiempirical
method produced a good balance between the computational
accuracy and cost, it was still not sufficient to accurately consider
highly conjugated systems. Therefore, to improve the rotational
potential energy along the bonds between the backbone units,
we obtained the REBG between the DFT and AM1 methods. Conse-
quently, we can describe the rotational dynamics and structural
variations of the backbone with the accuracy of DFT method. Based
on the results of the MD simulation, representative structures fre-
quently observed in MD trajectories were calculated to generate
the simulated UV–vis spectrum using the TDDFT method, and the
resulting UV–vis spectrum captured the characteristic features of
the experimental spectrum. Several crucial electronic and optical
properties were also analyzed which also support that several rep-
resentative structures of the stable conformers need to be consid-
ered to compare the experimental data at room temperature. We
expect that this approach will allow for a better outcome in terms
of time and accuracy in theoretical UV–vis spectrum analysis and
optoelectronic properties.
7
Journal of Molecular Liquids 341 (2021) 117406
CRediT authorship contribution statement
Md Al Mamunur Rashid: Formal analysis, Writing – original
draft, Writing – review & editing. Kyusang Ahn: Methodology,
Software, Formal analysis. Jonggu Jeon Methodolog: . Minhaeng
Cho: Writing – review & editing. BongSoo Kim: Visualization, Con-
ceptualization, Validation, Writing – review & editing. Kyung-Koo
Lee: Visualization, Writing –review & editing, Supervision. Kyung-
won Kwak: Visualization, Conceptualization, Writing – review &
editing, Formal analysis, Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
This work was supported by the National Research Foundation
of Korea (NRF) grant funded by the Korea government (MSIT)
(NRF-2020R1A5A1019141).
Appendix A. Supplementary material
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.molliq.2021.117406.
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