Materials Today Communications 33 (2022) 104688

Contents lists available at ScienceDirect

Materials Today Communications

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

Theoretical insight on model linear oligomers and their ring-fused analogs

used in organic electronics
Denisa Mastiľák Cagardová, Jan Matúška , Martin Michalík , Vladimír Lukeš *
Institute of Physical Chemistry and Chemical Physics, Slovak University of Technology, Radlinského 9, 81237 Bratislava, Slovakia

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

Keywords: Theoretical systematic study compares chemical and electronic structure of six series of linear aromatic oligo­
Aromaticity mers and their ring-fused analogs with various chain length of 5- and 6-membered rings. Chemical structure was
Conjugation described by structural HOMED and one-electron density topology EL aromaticity descriptors. The calculations
Heterocycles
demonstrated that the diradical electronic ground-state system is energetically preferred for larger six-membered
Molecular electronics
Oligomers
acenes where the electronic structure can be separated into two linear polyene chains. The influence of inter­
Organic electronics molecular interaction on the aromaticity perturbation in crystals was also analyzed for 20 available X-ray
structures. The aromaticity of central ring is lowered for longer molecules in solids. Next, the primary effect of
aromatic chain elongation on frontier orbital energies and vertical excitation energies was predicted. The
calculated data were correlated with experimental ones and polymer limits on investigated properties were
estimated.

1. Introduction
Unlike the traditional crystalline solar cells based on silicon photon
absorbers, one class of solar cells use organic compounds established on
π-conjugation and aromatic molecular structure [1]. Although the effi­
ciency of these cells is still low, just a little more than 10%, the reliable
low-cost fabrication of organic materials with different microstructure
and crystallinity is the important advantage in comparison with the
conventional silicon technology. Dependence of optoelectronic proper­
ties and electric charge carrier mobilities on molecular and crystal
structure is intensively studied [2–4] and it is even possible theoretically
predict chemical structure modification [5,6]. Currently, two major
classes of organic materials are applied in (opto)electronics [7]:
photoconductive polymers and low-molecular-weight semiconductors
with aromatic species. The latter can be efficiently purified, and it
usually forms ordered structures with high charge carrier mobilities.
Moreover, polymers containing ordered structural regions are also
suitable for fabrication of high-performance single-component devices.
Many properties connected with the electronic structure of oligomers
are chain-length dependent only up to certain length. Then, further
chain extension will not affect the investigated behavior in any signifi­
cant way. This aspect defines the role of conjugated oligomers as models
for the related polymers. The extrapolation of physical properties
towards infinite chain length and the description of a conjugated poly­
mer represents the key steps in a developing of suitable materials for
electronics. The electronic and optical properties of the polymers are
estimated through extrapolation of the data for oligomers, mostly done
either by an (empirical) exponential 3-parameter fit as introduced by
Meier et al. [8], or by the (physically founded) coupled oscillator
2-parameter model proposed by Kuhn [9], as reviewed earlier [10]. In
these models, the number of π-electrons, the number of aromatic rings or
the number of non-hydrogen atoms express the independent quantity
representing chemical structure. However, the aromaticity is a complex
multidimensional property, and the π-electron delocalization can be
quantified more exactly using aromaticity descriptors. Especially pop­
ular HOMA-based HOMED (Harmonic Oscillator Model of Electron
Delocalization) [11] and HOMHED (Harmonic Oscillator Model of
Aromaticity for Heterocyclic Electron Delocalization) [12] are indices
evaluated from theoretical or experimental X-ray bond lengths, respec­
tively. Next, the Bond Ellipticity (EL) aromaticity indices [13] are
calculated from the bond critical points which are evaluated using the
QTAIM (Quantum Theory of Atoms in Molecules) analysis [14]. These
aromaticity indices were successfully used for the description of chem­
ical structure of various small and large organic π-conjugated molecules
[15].
Most conjugated oligomers and polymers used as active materials in

* Corresponding author.
E-mail address: vladimir.lukes@stuba.sk (V. Lukeš).

https://doi.org/10.1016/j.mtcomm.2022.104688
Received 22 August 2022; Received in revised form 29 September 2022; Accepted 12 October 2022
Available online 15 October 2022
2352-4928/© 2022 Elsevier Ltd. All rights reserved.
D.M. Cagardová et al. Materials Today Communications 33 (2022) 104688

various organic electronic devices possess linear π-conjugated backbone

where simple or multiple aromatic rings are joined by single bonds. In
the last two decades, the compounds derived from phenylene, vinyl-
phenylene, fluorene and thiophene have attracted considerable atten­
tion. By attaching various side groups, energy gap between the frontier
molecular orbitals and optical properties can be altered. One major
disadvantage of these oligomeric structures is the deviation from
planarity through torsion around inter-ring bonds [16]. This deviation is
responsible for decreasing of electron delocalization along the π-conju­
gated backbone and less efficient intermolecular stacking in solid phase
or crystals. In this context, linear fusion of aromatic rings could be
effective way to extend the conjugation and support the more efficient
molecular packing [17]. Moreover, the linear fusion of benzene rings
can lead to one-dimensional molecular organic semiconductor possess­
ing an open-shell singlet ground state [18].
Although many theoretical and experimental works deal with the
dependence of optical or electric properties on the molecular backbone
elongation, the systematic analysis structural analysis that would
compare chemical structure of various linear oligomers and their ring-
fused analogs using the aromaticity indices was not performed yet.
Thus, in this paper, we decided to present theoretical DFT (Density
functional theory) calculations of six series of representative symmetric
linear oligomers and their ring-fused (condensed) analogs (Fig. 1). These
series include organic molecules, which are already commonly used in
the fields of electronics (tetracene, pentacene in Phn, α-sexithiophene in
oThn, polypyrroles as the Pyn, oligofurans as oFn [19], polyphenylenes
in oPhn [20], oligopyridines as oPn [21], etc.). Although the aromatic
poly- and oligo-selenophenes oSen are not used in electronics that
commonly yet, they can have some advantages over polythiophenes,
such as lower band gap, lower oxidation/reduction potentials and
higher polarizability of the selenium atom compared to sulfur and ox­
ygen leading to improved interchain charge transfer [22]. Although
theoretical studies dealing with some of these molecules exist (see also
Table S1), the systematic characterization of the local and global
aromaticity with respect to the molecular structure has not yet been
quantified. In this context, the partial aims of this study are: (1) to
compare singlet and triplet electronic ground state energies of studied
molecules; (2) to analyze the chemical structure of using structural
HOMED and Bond Ellipticity (EL) aromaticity indices; (3) to analyze the
influence of intermolecular interaction on the local and global aroma­
ticity perturbation in crystals for 20 available X-ray structures; (4) to
evaluate the dependence of Highest Occupied (HOMO) and Lowest
Unoccupied (LUMO) molecular orbital energies and optical band gaps.
Finally, the theoretical results will be compared with the available
experimental data and polymer limits corrected on experiment will be
presented.

2. Theoretical methods

2.1. Calculation details

All the calculations were performed by using Gaussian 16 program

package [23]. The density functional theory with 3-parameter hybrid
(U)B3LYP functional and the basis set 6–311 + +G* * were used for
geometries optimization as implemented in Gaussian 16 program
package. The process was performed by the tight optimization criteria
and ultrafine DFT integration grid. True minima on potential energy
surface were confirmed through vibrational analysis (no imaginary
frequencies present). For the basis of optimized geometries, the vertical
transition energies and oscillator strengths between the initial and final
states were computed in Gaussian 16 program package by the
Time-Dependent (TD)-DFT method with B3LYP and CAM-B3LYP func­
tionals. The Molekel program [24] was used for visualization of mo­ Fig. 1. Schematic structure and point groups of studied fused-ring molecules
and their oligomeric forms.
lecular geometries and frontier molecular orbitals. The experimental
X-ray geometries available for 20 studied molecules were taken from
Cambridge Structural Database [25].

2
D.M. Cagardová et al.
2.2. Aromaticity indices
The structural HOMED aromaticity index [12] for individual aro­
matic ring is expressed as:
( )2
1 ∑m
HOMED = 1 − αXY R(XY)ref − R(XY)i , (1)
m i=1
where m is the number of bonds considered in the studied aromatic ring
and R(XY)i is the bond length between X and Y atoms. The normalization
αXY constant for XY bond has been determined as follows [26].
αXY = 2 { ( R(XY)ref – R(XY)sin)2 + ( R(XY)ref – R(XY)doub)2}− 1⋅ (2)
The appropriate single Rsin, double Rdoub and reference aromatic
bond lengths Rref have been calculated from the DFT calculations of
benzene (CC bond), thiophene (CS bond), selenophene (CSe bond),
furan (CO bond) and pyrrole (CN(H) bonds).
Considered reference single (and double) bond lengths Rsin (Rdoub)
were obtained from DFT/B3LYP calculations of CH3–CH3 (CH2 =CH2)
for CC; (CH3)3–N (CH2 =N–CH3) for CN bonds; CH3–O–CH3 (CH2 =O)
for CO; CH3–S–CH3 (CH2 =S) for CS; CH3–Se–CH3 (CH2 =Se) for CSe.
The reference single, double, optimal bond lengths, and normalization
constants αXY used for the structural HOMED aromaticity indices are
collected in Table S2. In the case of HOMHED analysis, the reference
parameters obtained from X-ray were taken from the publication of
Frizzo and Martins [12] for CC, CN, CO and CS bonds (Table S3). For the
calculation of HOMHED indices, Eq. 1 is analogically used.
It is important to note that majority of studied molecules are sym­
metric and in case of the largest (10 rings) molecules, only 5 parameters
of HOMED(ring) are enough for local aromaticity description. The
QTAIM analysis was carried out by AIM All program package [14] and
the EL index based on one-electron density properties is obtained by
equation:
C∑ m ⃒ ⃒
EL = 1 − ⃒εi − εref ⃒ (3)
m i=1
where m has the same meaning as in the HOMED, and εi and εref are
QTAIM ellipticities in bond critical points (BCP) of actual bonds in
investigated molecule and in reference molecule, respectively. Accord­
ing to Dominikowska and Palusiak [13], C constant can be estimated as
follows:
1 ∑m ⃒ ⃒ based on chemical structure. This method takes only theoretical data for
C= ⃒εi − εref ⃒ (4)
m i=1
In this equation, m denotes number of bonds, εi denotes ellipticities
in BCPs of cyclo-hexa-1,3,5-triene bonds corresponding to single and
inner double bond length in (3E)-hexa-1,3,5-triene; and εref stands for
ellipticity in BCP of optimal bond length in benzene. In this case,
numerator and denominator can be divided by 3 to make equation
simpler, because for the evaluation of C, 6 investigated bonds (m = 6) of
cyclo-hexa-1,3,5-triene with bond lengths corresponding to 3 inner
double and 3 single bond lengths in (3E)-hexa-1,3,5-triene were used.
For the EL index, reference ellipticity values of 3E-cyclohexa-1,3,5-
triene bonds and corresponding calculated normalization constant C
[13] were used and they are presented in Table S4.
3. Results and discussion
All oligomers under study can be found in huge number of confor­
mations with respect to the mutual orientations of individual aromatic
rings. This makes the study of electronic and optical properties more
difficult since these quantities are usually significantly geometry
dependent. In our work, we have investigated symmetric conformations
with all-trans arrangement of X–C–C–X dihedral angles (X denotes het­
eroatom). These conformations correspond to the global minima at the
3
Materials Today Communications 33 (2022) 104688
potential energy surface. The point group symmetry of individual mol­
ecules is indicated in Fig. 1. Symmetry was kept in almost all studied
molecules excluded oPn series. However, molecules within oPn series
are common light-emitting conjugated polymers in optoelectronics (also
known as PPYs) [21] and obtained results are comparable with other
series. Fused molecules with favored trans orientations of heteroatoms
remained planar during geometry optimization.
On the other hand, oligomers, where the rings are connected by one
single inter-ring bond, are mostly distorted. Rings are deviated from the
plane symmetrically by the dihedral angle up to 40◦ for oligophenylenes
oPhn (see Table S5). For better imagination and understanding, opti­
mized geometries of all non-planar distorted molecules are visualized in
Fig. S1. As it can be seen from the figure, in the oligophenylenes (oPhn),
despite all ring deviate by about 40◦ , the main molecular axis has been
preserved. In contrast to that, the presence of heteroatoms in 5-
membered rings of oligomers (N, S, Se in oPyn, oSn, oSen, respec­
tively) causes destruction of the linearity of the main axis along the
molecular chain and the molecules bend. Molecular bending becomes
more significant with increasing chain length. Interestingly, for oFn and
oPn series employed DFT method predicts planar gas-phase geometries.
Preference of trans arrangement of heteroatoms obtained by DFT is
confirmed by available X-ray structures [25] (see Table S5). In contrast,
the molecular bending is not supported by X-ray structures. Probably
because the crystal latter stabilizes the molecules by intermolecular
interactions and causes planarization of monomer units.
The dependence of electronic energies for closed-shell and open-shell
diradical state of studied molecules is presented in Fig. S2. The diradical
systems were optimized using by unrestricted broken-symmetry DFT.
According to the published results [18], the diradical system is ener­
getically preferred for Ph9 and larger systems. The inclusion of nitrogen
atom shifts the preference to P12 and larger. For five membered acenes
and all investigated oligothiophenes, the singlet state is always ener­
getically preferred. The energy differences are higher than 150 kJ⋅mol–1
for acenes and 100–250 kJ⋅mol–1 for oligomers. Spin densities of Ph10
depicted in Fig. 2 indicates that the triplet ground state separates the
electronic structure into two linear polyacetylene chains. This prove the
hypothesis proposed by Bendikov et al [18]. Similar situation was found
for Ph11 and P10, P11 molecules containing nitrogen atoms (Fig. S3).
As it was mentioned in introduction part, the chemical structure of
studied molecules has been characterized using two types of aromaticity
indices based on two different principles. More common HOMA-based
HOMED index represent the first criterium of aromaticity description
both reference and studied molecules as input, in contrast to HOMHED,
when X-ray data are used for both reference and studied molecules. The
evaluated HOMED indices for individual aromatic rings of all molecules
are collected in Table S6. Local aromaticity characterized by HOMED
(ring) increases from ends towards to the center of molecule for majority
of series. Interestingly, in case of the largest molecules (7–10 rings) of
Phn and Pn series, a smaller decrease in the center of molecule occurs
(see Table S6). The exception from mentioned trend can be seen in Pyn
series, where a small decrease from ends towards the center is observed.
One possible explanation of this decrease might be connected with
hydrogen atoms bonded to nitrogen atoms. The hydrogen atoms are
slightly tilted, and this off-planarity causes small perturbation in
aromaticity (see Fig. S1).
In case of oligophenylenes, negligible differences in local aromaticity
of individual phenyl rings were found. The difference between the
number of aromatic rings and the total HOMED sum (ΣHOMED) gives
the information about the deviation from the ideal structural aroma­
ticity. For benzene molecule with perfect aromaticity, this deviation is
zero. Data collected in Table S6 reveal that the maximal deviations of
2.01 and 1.54 were found for P10 and oP10 molecules, respectively.
The chemical structure of a molecule in solid crystal is very often
affected by the interaction with neighboring molecules. These in­
teractions are additionally influenced by packing in the crystal lattice
D.M. Cagardová et al. Materials Today Communications 33 (2022) 104688

Fig. 2. Spin density of Ph10 molecule. The depicted surface is 0.035 a.u.

and dielectric properties of the crystal lattice. For example, if we
compare available X-ray structures with geometries of non-interacting
molecules, we may declare the role of intermolecular interactions in
planarization and the loss of molecular symmetry for larger molecules.
The evaluated HOMHED(ring) based on experimental data, collected in
Table S7, show the same trends in acenes - the local aromaticity of
central ring is slightly lowered for longer molecules. Interestingly,
opposite trend than in HOMED occurs in case of fused Thn. While
HOMED of individual rings increases towards the center of molecule,
HOMHED decreases. This is most likely caused by the significant influ­
ence of the surroundings of the monomer unit chosen from the X-ray
structure. Nevertheless, the differences between the ΣHOMHED and
ΣHOMED vales are minimal (see Table S6 and S7) and thus the global
aromaticity of molecules is affected minimally.
Various indices can be used for aromaticity characterization, but
suitable approach differs from series to series of organic molecules and
must be chosen carefully. Choosing more indices based on different
concepts is suggested to strengthen obtained results. Therefore, to sup­
port our findings, an ellipticity based EL index calculated by QTAIM
analysis was added. It is controlled by multiple parameters, not so
expensive nor time-consuming. EL indices are collected in Table S8.
Very often different aromaticity criteria may not correlate with each
other [27] because of fundamentally distinctive approaches. Neverthe­
less, in case of strictly topological indices such as HOMED and EL are,
very good linear dependence was found.
ΣEL = p + q × ΣHOMED
The p, q parameters for corresponding series are collected in Table 1
and the dependences are graphically illustrated in Fig. S4. Simple
recalculation between ΣHOMED and ΣEL indices is therefore possible as
well as with number of rings (Fig. S5).
Cyclic π-electron delocalization also results in molecular magnetic
property change. From this point of view, the Nucleus-Independent
Chemical Shifts (NICS) values can be used for the description of local
and global aromaticity. These indices are not always straightforward,
and their values depend considerably on the choice of molecular site.
Very often, NICSs are evaluated for the geometrical center of each aro­
matic ring requiring “ghost atoms”. The mutual comparison of our
evaluated HOMED indices with NICS indices published for selected
oligoacenes [28] and oligothiophenes [29] illustrates Fig. S6. The NICS
values for inner rings of acenes are lower than those at outer regions.
The more negative NICS values relate to the increase of magnetic ring
current. For example, the central ring of anthracene (–11.11 ppm)
exceeds the value of naphthalene (–8.41 ppm). Interestingly, the pre­
dicted NICS value for benzene ring indicate lower magnetic aromaticity
than for naphthalene rings [30]. Opposite behavior in local aromaticity
was reported by Radenkovic et al [28] for multicenter delocalization
indices (MCI) [31]. These indices reflect the extent of electron delocal­
ization among the set of N atoms and theoretically they should be
comparable with EL indices. However, the depicted trends in Fig. S7 do
not support this assumption. In case of oligothiophene series, where the
aromatic rings are not fused, the local aromaticity differences are
negligible. For example, the NICS parameter for all outer A rings are ca
− 12.3 ppm while as NICSs of the central rings are ca − 10.8 ppm (see
Fig. S6).
Since each of the local aromaticities of individual rings could
potentially be related to the excitation energies and energies of the
frontier molecular orbitals, multilinear regression is suggested as a
possible tool for correlation. If there is a such relation it can provide the
information on the interaction between the building blocks. Unfortu­
nately, the parameters obtained in such a regression had high p-values,
which makes them statistically irrelevant. For this reason, only global
aromaticity values will be further considered. For the main part of the
discussion, we will focus on ΣHOMED, while ΣEL is expected to yield
similar dependences due to the mutual correlation.
The energy levels of frontier molecular orbitals are valuable pa­
rameters for assessing the carrier injection ability as well as chemical
stability of investigated compounds. These energies should be close to
work function of inorganic electrodes in vacuum resulting in improve­
(5) ment of their p-type and n-type charge transport abilities. Based on the
optimized geometries, the B3LYP/6–311++G** energy levels of
HOMOs and LUMOs were calculated and depicted in Fig. 3. In case of
diradicals Phn and Pn, the RO-B3LYP molecular orbitals are depicted, i.
e., HOMO, LUMO and two Single Occupied Molecular Orbitals (SOMOs).
The energies of HOMO generally increase with the increasing molecular
size, e.g., from − 6.15 eV for Ph2 to − 4.33 eV for Ph10. On the other
hand, the LUMO energies decrease from − 1.40 eV (Ph2) to − 3.44 eV
(Ph10). According to Fig. 3, this trend can be seen for all series of
organic molecules in this study. As it was shown by Cagardová et al.
[32], following equation can be used to convert B3LYP theoretical

Table 1
Parameters of the correlation between the one-electron density ΣEL and the
structural ΣHOMED aromaticity indices. The symbol R denotes correlation co­
efficient. *Parameters of correlation was determined on reduced interval
(n = 4–10).
Series p q R Series p q R

Phn –0.157 0.623 0.998 oPhn 0.040 0.959 1.000

PhnT 0.106 0.635 0.997
Fn 0.048 –0.078 0.986 oFn –0.253 0.162 1.000
Thn –0.077 0.554 1.000 oThn –0.222 0.602 1.000 Fig. 3. Energy of HOMOs, SOMOs and LUMOs for studied molecular series.
Sen –0.191 0.602 1.000 oSen –0.241 0.613 1.000 Arrows show the direction of increasing n (number of rings in molecule).
Pyn 0.328 0.254 0.996 oPyn –0.001 0.519 1.000 Highlighted bands (cyan and yellow) are optimal ranges for HOMO and LUMO
Pn 0.229 0.429 0.999 oPn 0.693 1.000
energies of p- and n-type semiconductors, respectively. Symbol T denotes dir­
–0.025
PnT* 0.446 0.428 0.999
adical system.

4
D.M. Cagardová et al. Materials Today Communications 33 (2022) 104688

energies of frontier molecular orbitals to experimental ones:
EHOMO/LUMO
exp,cor = ( − 0.98 ± 0.21) + (0.81 ± 0.04) × EHOMO/LUMO
B3LYP
Chemical stability, mainly for n-type organic compounds is lowered
when exposed to the air. Therefore, optimal range of electrochemical
LUMO energies has been suggested to be lower than − 3.0 eV and higher
than − 4.4 eV [33,34]. However, the energies higher than − 3.9 eV are
responsible for more significant chemical instability against the oxida­
tion processes on the air. On the other hand, optimal values of HOMO
(6) energy for small molecules standardly used as p-type semiconductors are
from –4.9 to − 5.5 eV [35]. This range was set because the standard
counterpart metallic hole injecting electrodes have the comparable
ionization potentials. In Fig. 3, bands for the HOMO and LUMO optimal
ranges are highlighted (calculated from the above-mentioned

Fig. 4. Dependences of HOMO and LUMO energies on the ΣHOMED. The values in graphs represent the polymer limit values in eV. Symbol T in subscript denotes
diradical system.

5
D.M. Cagardová et al. Materials Today Communications 33 (2022) 104688

experimental values to theoretical ones by Eq. 6). As it can be seen, Table 2

HOMOs of commonly used p-type semiconductors, e.g., α-sexithiophene The polymer limit values of HOMO, LUMO energies and their differences *Eg in
(oTh6), tetracene (Ph4) or pentacene (Ph5) are within the suggested eV corrected on experiment (Eq. 6). Symbol T in subscript denotes diradical
range. Moreover, oligofurans (oF4 to oF9) and pentathienoacene (Th5), system.
as it was reported by Gidron et al. [36] and Xiao et al. [37], also show Eexp,cor Eexp,cor
p-type behavior. So, our calculations agree with previously published Series HOMO LUMO Eg Series HOMO LUMO Eg
results.
Phn –4.38 –3.90 0.49 oPhn –5.65 –2.47 3.18
The polymer limit values of the energies estimated for large (infinity) PhnT –4.37 –3.60 0.77
number of repeating units represent the next interesting information Fn –5.03 –2.90 2.13 oFn –4.88 –2.75 2.13
about the electronic structure. Exponential and Kuhn equations [9] are Thn –5.18 –2.94 2.24 oThn –5.06 –3.11 1.95
usually employed for this type of theoretical analysis involving standard Sen –5.10 –3.8 2.03 oSen –5.05 –3.26 1.79
Pyn 2.30 oPyn 2.61
fused molecules and oligomers. The number of rings [38], number of –3.77 –1.47 –4.54 –1.93
Pn –5.48 –4.88 0.60 oPn –5.93 –3.15 2.78
non-hydrogen atoms [39] or inverse analogs [38] were used as the in­ PnT –5.66 –4.10 1.54
dependent quantity. We found and evidenced linear dependence of
ΣHOMED on the number of rings (Fig. S5). These dependences can be
used for the ΣHOMED estimation of larger molecules without the need Proper investigation of optical band gaps requires comprehensive
for time-consuming geometry pre-optimalization and subsequent analysis of optical transitions. Band gap quantity determines the appli­
HOMED theory study as we did. Furthermore, the dependence of fron­ cability of organic compounds in optical devices. From the industrial
tier molecular orbital energies on the number of rings (n) was also point of view, the lowest energy transitions with the significant oscil­
determined to confirm the equivalence (Table S9a). In present study, lator strengths in visible light spectrum are investigated first. The data
global aromaticity index (ΣHOMED) as an equivalent to the number of collected in Table S11 reveal that the HOMO to LUMO excitation is
rings in molecule is advocated. Initially, we have tested the ability of dominantly S0→S1 transition with relatively high oscillator strengths
exponential and Kuhn function to describe properly the polymer limits comparing with the higher transitions. Energy increase with the mo­
for linear fused aromatic molecules. Acenes were examined in this test. lecular size can also be seen. Oligophenylenes have higher HOMO­
Dissimilarities between Kuhn and exponential equation are also illus­ →LUMO transition energy than fused acenes Phn. The same trend is
trated in Table S9. Even minor differences between fits of 9 points lead predicted for Pn/oPn series owing to its structural similarity (chain with
to enormous impact on the predicted limits. Kuhn equation failed to six-membered rings) with Phn/oPhn. On the other hand, opposite trend
estimate the frontiers energies for increasing n or ΣHOMED in all cases. was found for five-membered rings with heteroatoms. The exception
For example, for the dependence on n (Table S9a), Kuhn equation was observed for pyrrole-containing molecules Pyn/oPyn, where
reaches limits of usage, because to estimate a limit, parameter c in employed DFT method yielded negligible oscillator strengths for
equation should be equal or higher than –1. Moreover, LUMO energy HOMO→LUMO transition energies (highlighted in color in Table S11).
extrapolated this way becomes more negative than the energy of HOMO Therefore, higher vertical transitions with more significant oscillator
(crossing of the lines) and it leads to energy gap less than zero. strengths for these molecules are presented in Table S12 and are noted
Table S9b also shows both Kuhn and exponential fits as a function of the by asterisk in graphical demonstration of transition energies in Fig. 5. In
sum of HOMED, but the same problem with Kuhn equation occurs. case of diradical acenes, S0→S1 vertical transition consists of SOMOs to
Because of this, we decided to use three-parameter exponential fits. To LUMOs excitations. However, the oscillator strength is close to zero.
support our choice, validation for Ph20 molecule was done. For Therefore, we have collected the optical transition with relevant oscil­
B3LYP/6–311++G** optimal geometry of Ph20, found HOMO and lator strengths in Table S13. Based on our analysis of better suitability of
LUMO energies are − 4.28 eV and − 3.59 eV, respectively, with corre­ exponential fits, Eq. 7 analogy has been used for the estimation of
sponding energy gap of 0.69 eV (Table S9c). Exponential fit based polymer limits (ΣHOMED approaches to infinity) for the vertical tran­
frontiers energies for Ph20 presented in the third part of the table. sition energies and are noted in Fig. 5 next to the corresponding fits.
The chemical accuracy of theoretical excitation energies can be
EHOMO/LUMO = a + b × exp(c×ΣHOMED) (7) estimated from the comparison with the experimental UV/vis spectra.
are clearly in much better agreement with DFT values than Kuhn The experimental absorption maxima for oligomeric series oPhn, oFn
and oThn measured in solvent are collected in Table S14. The calculated
extrapolation-based ones. Thus, the exponential fit is more appropriate
for further discussion. TD-B3LYP HOMO→LUMO transition energies (Table S11) are slightly
underestimated for the longer oligomers. However, energies obtained by
The dependences of theoretical HOMO, LUMO energies and their
differences Eg on ΣHOMED indices are depicted in Fig. 4 and Fig. S8, TD-CAM-B3LYP approach are in better agreement with experimental
data (see Table S11). The correlation of available experimental energies
respectively. The parameters of exponential function (see Eq. 7) are
collected in Table S10. It can be seen, that oligophenylenes (oPhn) have (Table S14) for the oligofurans, oligothiophenes and oligophenylenes
with TD-B3LYP and TD-CAM-B3LYP theoretical energies leads to the
higher LUMO and lower HOMO than their fused analogs (Phn) resulting
in higher energy gaps. In contrast to that, heterocyclic oligomers bearing linear dependences (see Fig. S9a)
oxygen, sulfur or selenium (oFn, oThn or oSen, respectively) have EHOMO→LUMO (oligomers) = 0.983 + 0.810 × EHOMO→LUMO (8)
exp,cor TD− B3LYP
smaller energy gaps than their fused analogs (Fn, Thn or Sen, respec­
tively). The series of pyrrole derivatives Pyn/oPyn exhibit the specific EHOMO→LUMO (oligomers) = 0.528 + 0.851 × EHOMO→LUMO (9)
behavior, i.e., HOMOs and LUMOs for fused series are both higher than
exp,cor TD− CAM− B3LYP

their oligomeric forms. Mutual comparison of Pn and oPn series is more
troublesome, but energy gaps have the same trend as Phn/oPhn, thus
the oligomeric series reach higher values of Eg. In case of diradicals,
SOMOs and LUMO tends to reach common limit value − 3.24 eV and
–3.85 for Phn and Pn respectively.
The experimental electrochemical gap of optoelectronic organic
compounds and their electrical conductivity is directly affected by
HOMO− LUMO energy gap (Eg). Theoretical polymer limit values cor­
rected to experimental ones (using Eq. 6) are listed in Table 2.
with correlation coefficients of 0.981 (TD-B3LYP) and 0.989 (TD-CAM-
B3LYP).
Interestingly, acenes series Phn offer broader range of optical tran­
sition energies than oligophenylenes oPhn. For example, TD-CAM-
B3LYP energies of HOMO→LUMO transitions vary from ultraviolet re­
gion of 4.66 eV for Ph2 to near-infrared region of 1.00 eV for Ph10. The
TD-CAM-B3LYP theoretical values for small acenic molecules agree
better with available experimental data (Tables S14 and S15) than TD-
B3LYP as well as in oligomeric series. The same occurs in case of

6
D.M. Cagardová et al. Materials Today Communications 33 (2022) 104688

Fig. 5. The dependence of vertical TD-B3LYP and TD-CAM-B3LYP excitation energies EHOMO→LUMO on the ΣHOMED indices. The values in graphs represent the
polymer limit values in eV. Higher vertical transition energies with more significant oscillator strengths are noted by asterisk.

condensed thiophenes Thn.

Table 3
Correlation of experimental energies available for these fused series
The predicted polymer limit values of optical HOMO-LUMO band gaps corrected
of acenes and thiophenes with theoretical ones also leads to the linear
on experiment in eV (Eqs. 8 to 11). Symbol T in subscript denotes diradical
dependences (see Table 3 and Fig. S9b): system.
EHOMO→LUMO
exp,cor (fused) = 0697 + 0.881 × EHOMO→LUMO
TD− B3LYP (10) Series B3LYP CAM-B3LYP Series B3LYP CAM-B3LYP

Phn 0.96 0.98 oPhn 3.79 3.97

EHOMO→LUMO
exp,cor (fused) = 0.338 + 0.905 × EHOMO→LUMO
TD− CAM− B3LYP (11) PhnT 1.22 1.35
Fn 2.93 3.15 oFn 2.82 2.89
Thn 2.88 2.99 oThn 2.65 2.71
with correlation coefficients of 0.993 and 0.995 for TD-B3LYP and TD-
Sen 2.63 2.74 oSen 2.51 2.54
CAM-B3LYP, respectively. Pyn 2.99 3.03 oPyn 3.25 3.34
The dependences of theoretical HOMO-to-LUMO excitation energies Pn 1.21 1.13 oPn 3.43 3.59
on ΣHOMED indices are depicted in Fig. 5 (with above-mentioned ex­ PnT 1.53 1.56
ceptions for (o)Pyn, where higher transitions with more significant

7
D.M. Cagardová et al.
strengths are used). The parameters of exponential functions are
collected in Table S16.
Experimental optical band gaps were predicted using theoretical TD-
B3LYP and TD-CAM-B3LYP energies (Table S15) employing Eqs. 8 to 11
and are listed in Table 3. Generally, the estimated optical band gap
descends in following order: oPh∞ > oP∞ > oPy∞ > oF∞ > oTh∞
> oSe∞. The experimental optical band gaps measured for polypyrroles,
polyfurans and polythiophenes are 3.2 [40], 3.0, and 2.5–2.7 eV [41,
42], respectively. These experiments are dependent on the sample pro­
cessing and polymer morphology. The maximal difference between the
corrected theoretical values calculated for ideal polymer and available
experimental data was found for polypyrrole (0.14 eV). Probably, the
smaller optical band gap of real polymer chain can relate to higher
planarity structure comparing with our model oligomer. For fused se­
ries, the order of estimated optical band gaps differs and descends as Py∞
> F∞ > Th∞ > Se∞ > P∞ > Ph∞ (see Table 3). Nevertheless, the
extraction of polymer properties from oligomer calculations represents
more complex theoretical problem [43,44] dependent on the used
approach. For example, the VASP simulations based on the plane-waves
with inclusion of periodic boundary conditions give lower energy limits,
i.e., 1.86 eV for oP∞, 1.04 eV for oTh∞ and 1.70 eV for oPy∞ [45].
4. Conclusions
A theoretical study was focused on the series of representative linear
oligomers and their ring-fused analogs build by 5- and 6-membered
rings. Considering the chemical structure, oligomerization signifi­
cantly disrupts planarity for majority of studied molecules. Interestingly,
oligofurans remain planar. The quantum chemical calculations show
that the diradical electronic ground-state system is energetically
preferred for larger six-membered acenes. The presence of nitrogen
atoms in molecular skeleton suppresses the stability of electronic triplet
ground-state. For linearly fused five membered aromatic rings, the
electronic singlet state is always energetically preferred because the
electronic structure cannot be separated into two linear polyene chains.
Perfect equivalency of the aromaticity parameters with the number
of rings in molecules was proved. Correlations of various structural,
electronic, and spectroscopic properties on global aromaticity were
found. The analysis of the aromaticity was based on structural HOMED
and one-electron density topology EL aromaticity descriptors. Very good
linear dependences between the cumulative structural ΣHOMED indices
and ΣEL indices based on one-electron density properties were demon­
strated for individual series of molecules. For 20 available X-ray struc­
tures of studied molecules, the structural HOMHED indices were
evaluated and compared with theoretical HOMED ones. The primary
influence of aromatic chain elongation on frontier orbital energies and
vertical excitation energies was discussed in terms of the global
aromaticity. Increase in molecular size has different influence on elec­
tronic properties with respect to the presence of heteroatoms and ring
addition. The polymer limits of frontiers energies were evaluated from
the three-parameter exponential fits where the cumulative ΣHOMED
was used as the independent quantity. The Kuhn’s equation seems not to
be suitable for fused series. Based on the comparison and correlation
with the available experimental data, electrochemical band gap limits
were estimated. Moreover, expected spectroscopic behavior was pre­
dicted and discussed for all studied molecules and linear dependence
was found. Our theoretical results help to provide a fundamental un­
derstanding of structural elongation effects on investigated properties
and will be used as the reference data for the investigation of novel
molecules with extended two-dimensional and three-dimensional aro­
matic structures enabling the perspective design of high-performance
organic solar cells and optoelectronic devices.
CRediT authorship contribution statement
Denisa Mastiľák Cagardová: Calculations, Data processing. Jan
8
Materials Today Communications 33 (2022) 104688
Matúška: Visualization, Investigation, Data processing. Martin
Michalík: Software, Validation, Writing – editing. Vladimír Lukeš:
Conceptualization, Methodology, Writing – editing, Supervision.
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.
Data availability
Data will be made available on request.
Acknowledgments
The work has been supported by Slovak Research and Development
Agency (APVV-19-0024) and by Ministry of Education, Science,
Research and Sport of the Slovak Republic (VEGA 1/0461/21). V.L.
thanks to Ministry of Education, Science, Research and Sport of the
Slovak Republic for funding within the scheme “Excellent research
teams". We are grateful to the HPC center at the Slovak University of
Technology in Bratislava, which is a part of the Slovak Infrastructure of
High-Performance Computing (SIVVP project, ITMS code
26230120002, funded by the European region development funds,
ERDF) for the computational time and resources made available.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.mtcomm.2022.104688.
References
[1] A. Pron, P. Gawrys, M. Zagorska, D. Djurado, R. Demadrille, Electroactive materials
for organic electronics: preparation strategies, structural aspects and
characterization techniques, Chem. Soc. Rev. 39 (2010) 2577–2632, https://doi.
org/10.1039/b907999h.
[2] A. Mohajeri, M. Farmani, Toward more efficient organic semiconductors: the
relationship between morphology, charge transport, and photophysical properties,
Appl. Electron. Mater. 4 (2022) 246–258, https://doi.org/10.1021/
acsaelm.1c00975.
[3] S. Ghomrasni, S. Ayachi, K. Alimi, New acceptor–donor–acceptor (A–D–A) type
copolymers for efficient organic photovoltaic devices, J. Phys. Chem. Solids 76
(2014) 105–111, https://doi.org/10.1016/j.jpcs.2014.08.013.
[4] S.G. Dutremez, X. Dumail, S. Mallet-Ladeira, A. Van Der Lee, D. Granier,
N. Masquelez, J.-S. Filhol, Pentafluorophenylphosphonic acid as a new building
block for molecular crystal fabrication, Cryst. Growth Des. 21 (2021) 2028–2045,
https://doi.org/10.1021/acs.cgd.0c01402.
[5] M. Mbarek, M. Chemek, J. Wery, J.L. Duvail, K. Alimi, The effect of conjugation
length distribution on the properties of modified PPV, J. Phys. Chem. Solids 75
(2014) 752–758, https://doi.org/10.1016/j.jpcs.2014.02.006.
[6] P.A. Praveen, A. Bhattacharya, T. Kanagasekaran, A. DFT, study on the electronic
and photophysical properties of biphenylyl/ thiophene derivatives for organic light
emitting transistors, Mater. Today Commun. 25 (2020), 101509, https://doi.org/
10.1016/j.mtcomm.2020.101509.
[7] O. Ostroverkhova, Organic optoelectronic materials: mechanisms and applications,
Chem. Rev. 116 (2016) 13279–13412, https://doi.org/10.1021/ACS.
CHEMREV.6B00127/SUPPL_FILE/CR6B00127_SI_001.PDF.
[8] H. Meier, U. Stalmach, H. Kolshorn, Effective conjugation length and UV/vis
spectra of oligomers, Acta Polym. 48 (1997) 379–384, https://doi.org/10.1002/
ACTP.1997.010480905.
[9] W. Kuhn, Über das Absorptionsspektrum der Polyene, Helv. Chim. Acta 31 (1948)
1780–1799, https://doi.org/10.1002/HLCA.19480310644.
[10] M. Wykes, B. Milián-Medina, J. Gierschner, Computational engineering of low
bandgap copolymers, Front. Chem. 1 (2013) 35, https://doi.org/10.3389/
FCHEM.2013.00035/BIBTEX.
[11] E.D. Raczyńska, M. Hallman, K. Kolczyńska, T.M. Stepniewski, On the harmonic
oscillator model of electron delocalization (HOMED) index and its application to
heteroatomic π-electron systems, Symmetry 2 (2010) 1485–1509, https://doi.org/
10.3390/SYM2031485.
[12] C.P. Frizzo, M.A.P. Martins, Aromaticity in heterocycles: new HOMA index
parametrization, Struct. Chem. 23 (2012) 375–380, https://doi.org/10.1007/
s11224-011-9883-z.
D.M. Cagardová et al.
[13] J. Dominikowska, M. Palusiak, EL: the new aromaticity measure based on one-
electron density function, Struct. Chem. 23 (2012) 1173–1183, https://doi.org/
10.1007/s11224-011-9941-6.
[14] T.A. Keith, AIMALL (Version 14.04.17), AIMALL (Version 14.04.17), TK Gristmill
Software, Overl. Park KS, USA (2019).
[15] U.H.F. Bunz, N-Heteroacenes, Chem. Eur. J. 15 (2009) 6780–6789, https://doi.
org/10.1002/chem.200900990.
[16] S.M. Bouzzine, S. Saı¨d Bouzakraoui, M. Bouachrine, M. Hamidi, Density functional
theory (B3LYP/6–31 G*) study of oligothiophenes in their aromatic and polaronic
states, J. Mol. Struct. Theochem. 726 (2005) 271–276, https://doi.org/10.1016/j.
theochem.2005.04.023.
[17] C. Tönshoff, H.F. Bettinger, Pushing the limits of acene chemistry: the recent surge
of large acenes, Chem. Eur. J. 27 (2021) 3193–3212, https://doi.org/10.1002/
CHEM.202003112.
[18] M. Bendikov, H.M. Duong, K. Starkey, K.N. Houk, E.A. Carter, F. Wudl,
Oligoacenes: theoretical prediction of open-shell singlet diradical ground states,
J. Am. Chem. Soc. 126 (2004) 7416–7417, https://doi.org/10.1021/ja048919w.
[19] O. Gidron, M. Bendikov, α-Oligofurans: an emerging class of conjugated oligomers
for organic electronics, Angew. Chem. Int. Ed. 53 (2014) 2546–2555, https://doi.
org/10.1002/ANIE.201308216.
[20] X. Guo, M. Baumgarten, K. Müllen, Designing π-conjugated polymers for organic
electronics, Prog. Polym. Sci. 12 (2013) 1832–1908, https://doi.org/10.1016/J.
PROGPOLYMSCI.2013.09.005.
[21] J. Tao, S. Tretiak, J.X. Zhu, Prediction of excitation energies for conjugated
oligomers and polymers from time-dependent density functional theor, Materials 3
(2010) 3430–3467, https://doi.org/10.3390/MA3053430.
[22] S.S. Zade, N. Zamoshchik, M. Bendikov, Oligo- and polyselenophenes: a theoretical
study, Chem. Eur. J. 15 (2009) 8613–8624, https://doi.org/10.1002/
CHEM.200900971.
[23] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman,
G. Scalmani, V. Barone, G.A. Petersson, H. Nakatsuji, X. Li, M. Caricato, A.
V. Marenich, J. Bloino, B.G. Janesko, R. Gomperts, B. Mennucci, H.P. Hratchian, J.
V. Ortiz, A.F. Izmaylov, J.L. Sonnenberg, D. Williams-Young, F. Ding, F. Lipparini,
F. Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson, D. Ranasinghe, V.
G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang, M. Hada, M. Ehara, K. Toyota,
R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai,
T. Vreven, K. Throssell, J. Montgomery, J. A, J.E. Peralta, F. Ogliaro, M.
J. Bearpark, J.J. Heyd, E.N. Brothers, K.N. Kudin, V.N. Staroverov, T.A. Keith,
R. Kobayashi, J. Normand, K. Raghavachari, A.P. Rendell, J.C. Burant, S.S. Iyengar,
J. Tomasi, M. Cossi, J.M. Millam, M. Klene, C. Adamo, R. Cammi, J.W. Ochterski,
R.L. Martin, K. Morokuma, O. Farkas, J.B. Foresman, D.J. Fox, Gaussian 16, Rev.
B.01, Gaussian, Inc., Wallingford, CT, 2016.
[24] U. Varetto, Molekel 5.4. 0.8, Swiss Natl. Supercomput. Centre, Manno, Switz
(2009).
[25] C.R. Groom, I.J. Bruno, M.P. Lightfoot, S.C. Ward, The Cambridge structural
database, Acta Crystallogr. Sect. B Struct. Sci. Cryst. Eng. Mater. 72 (2016)
171–179, https://doi.org/10.1107/S2052520616003954.
[26] B. Ośmiałowski, E.D. Raczyńska, T.M. Krygowski, Tautomeric equilibria and pi
electron delocalization for some monohydroxyarenes-quantum chemical studies,
J. Org. Chem. 71 (2006) 3727–3736, https://doi.org/10.1021/JO052615Q/
SUPPL_FILE/JO052615QSI20060317_111825.PDF.
[27] H. Szatylowicz, O.A. Stasyuk, M. Solà, T.M. Krygowski, Aromaticity of nucleic acid
bases, Wiley Interdiscip. Rev. Comput. Mol. Sci. 11 (2021), e1509, https://doi.org/
10.1002/WCMS.1509.
[28] S. Radenković, J. Đurđević, P. Bultinck, Local aromaticity of the five-membered
rings in acenaphthylene derivatives, Phys. Chem. Chem. Phys. 14 (2012) 14067,
https://doi.org/10.1039/c2cp41472d.
Materials Today Communications 33 (2022) 104688
[29] D. Valencia, G.T. Whiting, R.E. Bulo, B.M. Weckhuysen, Protonated thiophene-
based oligomers as formed within zeolites: understanding their electron
delocalization and aromaticity, Phys. Chem. Chem. Phys. 18 (2016) 2080–2086,
https://doi.org/10.1039/C5CP06477E.
[30] P.V.R. Schleyer, C. Maerker, A. Dransfeld, H. Jiao, N.J.R. Van Eikema Hommes,
Nucleus-independent chemical shifts: a simple and efficient aromaticity probe,
J. Am. Chem. Soc. 118 (1996) 6317–6318, https://doi.org/10.1021/ja960582d.
[31] M. Giambiagi, M. Segre de Giambiagi, C.D. dos Santos Silva, A. Paiva de
Figueiredo, Multicenter bond indices as a measure of aromaticity, Phys. Chem.
Chem. Phys. 2 (2000) 3381–3392, https://doi.org/10.1039/b002009p.
[32] D. Cagardová, J. Matúška, M. Michalík, P. Poliak, V. Lukeš, Theoretical
comparative study of promising semiconducting aromatic molecules and their
fluorinated counterparts, Synth. Met. 260 (2020), 116263, https://doi.org/
10.1016/J.SYNTHMET.2019.116263.
[33] Y.C. Chang, M.Y. Kuo, C.P. Chen, H.F. Lu, I. Chao, On the air stability of n -channel
organic field-effect transistors: a theoretical study of adiabatic electron affinities of
organic semiconductors, J. Phys. Chem. C 114 (2010) 11595–11601, https://doi.
org/10.1021/JP1025625.
[34] A.R. Murphy, J.M.J. Fréchet, Organic semiconducting oligomers for use in thin film
transistors, Chem. Rev. 107 (2007) 1066–1096, https://doi.org/10.1021/
CR0501386.
[35] J. Filo, M. Putala, Semiconducting organic molecular materials, J. Electr. Eng. 61
(2010) 314–320, https://doi.org/10.2478/V10187-010-0050-3.
[36] O. Gidron, A. Dadvand, E. Wei-Hsin Sun, I. Chung, L.J.W. Shimon, M. Bendikov, D.
F. Perepichka, Oligofuran-containing molecules for organic electronics, J. Mater.
Chem. C 1 (2013) 4358–4367, https://doi.org/10.1039/C3TC00079F.
[37] K. Xiao, Y. Liu, T. Qi, W. Zhang, F. Wang, J. Gao, W. Qiu, Y. Ma, G. Cui, S. Chen,
X. Zhan, G. Yu, J. Qin, W. Hu, D. Zhu, A highly π-stacked organic semiconductor for
field-effect transistors based on linearly condensed pentathienoacene, J. Am.
Chem. Soc. 127 (2005) 13281–13286, https://doi.org/10.1021/JA052816B/
SUPPL_FILE/JA052816BSI20050726_080020.PDF.
[38] R.E. Larsen, Simple extrapolation method to predict the electronic structure of
conjugated polymers from calculations on oligomers, J. Phys. Chem. C 120 (2016)
9650–9660, https://doi.org/10.1021/ACS.JPCC.6B02138/SUPPL_FILE/
JP6B02138_SI_001.PDF.
[39] A. Musa, M.A. Saeed, A. Shaari, R. Sahnoun, M. Lawal, Effects of delocalised
π-electrons around the linear acenes ring (n = 1 to 7): an electronic properties
through DFT and quantum chemical descriptors, Mol. Phys. 113 (2015)
1347–1358, https://doi.org/10.1080/00268976.2014.993734.
[40] K. Yakushi, L.J. Lauchlan, T.C. Clarke, G.B. Street, Optical study of polypyrrole
perchlorate, J. Chem. Phys. 79 (1998) 4774, https://doi.org/10.1063/1.445621.
[41] S. Glenis, M. Benz, E. LeGoff, M.G. Kanatzidis, J.L. Schindler, C.R. Kannewurf,
Polyfuran: a new synthetic approach and electronic properties, J. Am. Chem. Soc.
115 (1993) 12519–12525, https://doi.org/10.1021/JA00079A035.
[42] T.C. Chung, J.H. Kaufman, A.J. Heeger, F. Wudl, Charge storage in doped poly
(thiophene): optical and electrochemical studies, Phys. Rev. B 30 (1984) 702,
https://doi.org/10.1103/PhysRevB.30.702.
[43] A. Pomogaeva, B. Kirtman, F.L. Gu, Y. Aoki, Band structure built from oligomer
calculations, J. Chem. Phys. 128 (2008), 074109, https://doi.org/10.1063/
1.2840354.
[44] C.X. Cui, M. Kertesz, Y. Jiang, Extraction of polymer properties from oligomer
calculations, J. Phys. Chem. 94 (1990) 5172–5179, https://doi.org/10.1021/
j100375a074.
[45] S. Yang, P. Olishevski, M. Kertesz, Bandgap calculations for conjugated polymers,
Synth. Met. 141 (2004) 171–177, https://doi.org/10.1016/j.
synthmet.2003.08.019.