Journal of Molecular Structure 1274 (2023) 134484

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Journal of Molecular Structure

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

Effect of heteroatoms on structural, electronic and spectroscopic

properties of polyfuran, polythiophene and polypyrrole: A hybrid DFT
approach
Asma Hassan a, Muhammad Ismail a, Ali H. Reshak b,c,d,∗, Zeshan Zada e, Abdul Ahad Khan f,
Fazal Ur Rehman M g, Muhammad Arif h, Khadija Siraj a, Shafqat Zada i, G. Murtaza j,k,
Muhammad M. Ramli c
a
Department of Chemistry, Women University Swabi, Swabi 23430, KP, Pakistan
b
Physics Department, College of Science, University of Basrah, Basrah 61004, Iraq
c
Center of Excellence Geopolymer and Green Technology (CEGeoGTech), University Malaysia Perlis, 01007 Kangar, Perlis, Malaysia
d
Department of Instrumentation and Control Engineering, Faculty of Mechanical Engineering, CTU in Prague, Technicka 4, 616607 Prague, Czechia
e
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
f
Department of Physics, University of Peshawar, KP, Pakistan
g
Department of Chemistry, Lahore Garrison University, Pakistan
h
Department of Physics, Abdul Wali Khan University, Mardan, Pakistan
i
Department of bioChemistry, Quaid e azam University of Islamabad, Pakistan
j
Materials Modelling Lab, Department of Physics, Islamia College University, Peshawar, Pakistan
k
Department of Mathematics & Natural sciences, Prince Mohammad Bin Fahd University, P. O. Box 1664, Alkhobar 31952, Saudi Arabia

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

Article history: In the present manuscript a brief discussion about the new generation of plastic or polymer also called
Received 18 August 2022 materials of 21st century was conducted. A comparative study of the structural, electronic and spectro-
Revised 30 October 2022
scopic properties of the three heterocyclic polymers polypyrrole, polythiophene and polyfuran in neutral
Accepted 2 November 2022
form of particular interest has been carried out using the result of Density Function Theory B3LYP/6-
Available online 3 November 2022
31G (d, p) methods. Also how theoretical methods utilizing quantum chemical calculations can be em-
Keywords: ployed to study various properties of these new generation polymers and what information’s can be
Heteroatoms drawn from them about their structural and electronic properties has been discussed. Our major concern
Spectroscopic is to study the effect of heteroatom i-e O, N, S on electronic, structural and spectroscopic properties of
Polyfuran Furans, Pyrrole and Thiophenes. For this purpose, the important structural properties (geometric parame-
Polythiophene ters, charge analysis) spectroscopic properties (vibrational and VU–vis spectra’s) and electronic properties
Polypyrrole
(HOMO, LUMO and band gap) of these polymers are compared. The calculated trend in the values of
Hybrid DFT Approach
different properties (electronic, structural and spectroscopic) of the polymers is an excellence agreement
with available experimental values. The theoretical calculation predicted the order of more attraction
as polythiophene (PTh) ˃ polyfuran (PF) ˃ polypyrrole (PPy) from optimized geometric parameters, the
Spectroscopic study predict that the λmax absorption shown in the order of PTh ˃ PF ˃ PPy, the HOMO,
LUMO and band gap calculation also go side by side with the result obtained from structural and spec-
troscopic properties calculation
© 2022 Elsevier B.V. All rights reserved.

1. Introduction

1.2. Conducting polymers

For long time, polymers were used as insulating materials and

considered that polymers do not conduct electricity but more than
∗
Corresponding author at: Department of Instrumentation and Control Engineer- a Decade now that certain classes of polymers which show conju-

ing, Faculty of Mechanical Engineering, CTU in Prague, Technicka 4, 616607 Prague, gation (posses’ conjugation along the polymers backbone) be-
Czechia. 
have like a semiconductor. The presence of delocalization of
E-mail address: maalidph@yahoo.co.uk (A.H. Reshak).

https://doi.org/10.1016/j.molstruc.2022.134484
0022-2860/© 2022 Elsevier B.V. All rights reserved.
A. Hassan, M. Ismail, A.H. Reshak et al. Journal of Molecular Structure 1274 (2023) 134484

Fig. 1. Chemical structure of PF(a), PTh(b) and PPy(c).

electrons, polymers are able to conduct electricity called conduct- ductivity of PPy was exhibited in 1968 [14,15]. Due to some aston-
ing polymers. Conduct ing polymers act as substitutes for naturally ishing properties like high flexibility, high conductivity, stabilizes
conductive material [1]. Therefore, the π - electrons play a key role oxidize form, water soluble, superior redox properties, and valu-
to determine the electrical conductivity and band structure of con- able optical properties, PPy is widely studied C.Ps as both theo-
ducting polymers(2). Conducting polymers have a huge interest in retically and experimentally [16]. PPy can be synthesized chemi-
the quest for tough, cheap, flexi ble electronic circuit. Conducting cally and electrochemically. Due to the above properties PPy have
polymers (C.Ps) have many interesting electrical, electrochemical, a large scale of application such as a biosensor, gas sensor [17],
structural, mechanical and optical properties. Due to their interest- actuator, super capacitor etc [18].
ing properties C.Ps received a great attention towards its discovery. PTh is another very interesting conjugated C.Ps [19]. Like PPy,
Discovering C.Ps in the late 1970s by Dr. Hideki Shirakawa, Alan PTh is also a heteroatomic polymer, but in PTh sulfur is the het-
Jay Heega and Graham MacDiarmid at university of Pennsylvania eroatom in the backbone. PTh is the second generation of C.Ps. The
received Nobel prize in 20 0 0 [3]. After discovery of C.Ps scientist structure of (PTh), as shown in Fig, is linear and conjugated hetero-
found many applications to the newly C.Ps, such as sensor tech- cyclic[20]. Like PPy, PTH is very important conjugated polymer due
nology, electrochemical devices, super capacitors, construction of to some properties like storage stability, high electrical conductiv-
Photovoltaic cell, making of re- chargeable batteries, biomedical, ity, environmental stability, low weight, good redox ability [21].
artificial nerves etc [4]. Conjugated heterocyclic polymers like (PF), PTh has a large scale of applications especially solar cell [22], elec-
(PPy), (PTh), are very important class of C.Ps [5]. These polymers trochemical display devices, receptor for detecting chiral molecule
studied both, theoretically and experimentally have drawn special etc [23]. PTh results from the polymerization of thiophenes and
interest in the field of nanoscience and nanotechnology [6]. Among be- comes conducting when electrons removed or added from the
these C.Ps (PPy) and (PTh) are the most widely studied C.Ps be- orbital via dopant [24].
cause (PPy) and (PTh) show high conductivity upon doping, chem- Polyfuran is a five member hetetroatomic ring compound hav-
ical stability and nonlinear optical properties [7]. However Polyfu- ing four carbon atoms and one heteroatom (oxygen). Among the
ran attracted less attention because polyfuran showed some dif- heterocyclic polymers such as PPy and PTh, Polyfuran is less stud-
ficulties in synthesis [7,8]. The Conducting polymers (CPs) have ied C.P because it exhibits low conductivity, high oxi dation poten-
drawn significant interest of researchers for more than 30 years tial and difficult in synthesis [25]. The structure of PF is analogous
because of their economic importance, superior stability, lighter to PPy and PTh but the heteroatom (S, NH) is replaced by oxygen
weight, better workability, resistance to corrosion and satisfac- in PF. The structure of PF is shown in Fig. 1. PF can be synthe-
tory electrical conductivity. Some applications of CPs are: recharge- sized chemically and electrochemically in organic media. In 1964
able batteries, electro chromic display devices, light reflecting or PF was synthesized chemically, while synthesizing electrochemi-
light transmitting appliances for optical information, sensors and cally by polymerization of furan has been developed in the past
storage for glare reduction systems and smart windows in auto- decade. Polyfuran is slightly soluble in water and highly volatile
mobiles and buildings, polymeric light emitting diodes (PLEDs), organic compound [26]. PF although has attracted less attention
photovoltaic devices, transistors, electromagnetic shielding against than PPy and PTh but still has many industrial ap plications in in-
electro-magnetic interferences (EMI) and printed electronic circuits sulating form and much technological application in resin form and
[9]. The chemical structure of PPy, PTh, PF are shown in Fig. 1 be- conversion of solar energy into photo voltaic [27].
low.
Polypyrol is a type of conjugated organic polymers. Among the 2. Computational details
various C.Ps, PPy have attracted special interest because of their
high conductivity [10–12]. PPy has heteroatomic polymers having Density function theory (DFT) hybrid function [Becke 3-
nitrogen as heteroatom in their five-member ring. The chemical Parameters (Ex- change), Lee, Yang and parr] B3LYP [28] were
structure of PPy is given in Fig. 1. In 1960 the conjugated organic employed for the study of geometric, spectroscopic and electron-
polymers family received PPY by the pyrolysis of tetraiodopyrol ics properties of PPy, PTh and PF. Stimulated all these prop-
[13]. PPy conduct electricity in the presence of dopant. The con- erties by using split valence basis set (6-31G∗∗ ). All calculation
were carried out by using Gaussian 09 and analyzed the result

2
A. Hassan, M. Ismail, A.H. Reshak et al. Journal of Molecular Structure 1274 (2023) 134484

Fig. 2. Optimized bond length of PPy, PF and PTh where n=1...9 repeating units.

by using Gabediet [29] and Gaussian view [30]. nPPy, nPTh and paring the optimized geometry of PF, PPy, and PTh it is indicated
nPF(n=1,2,3,4,5,6,7,8,9) conducting polymers were used (n repre- that the optimized geometry of PF and PPy is in the range of 1.3
sent ring number). For geometrical optimization of PPy, PTh, and and that of PTh is in the range of 1.7 which show that the PF and
PF the above mentioned level is used to calculate the parameters PPy show small bond alteration with each other while PTh show
(bond angle and bond length). Further simulation such as spectro- large bond alteration with PF and PPy in neutral form. According
scopic (UV and IR), Mullikan charge analysis, Natural bond orbital to our theoretically calculated data (Tables 1, 2, 3) the increase in
(NBO) analysis, Highest occupied molecular orbital (HOMO), Low- bond length of PF, PPy [32] and PTh is in the or der of PTh ˃ PPy ˃
est unoccupied molecular orbital(LUMO) and band gap calculation PF. The intermediate bond length distance from monomer unit to
of PPy, PTh, PF were carried out by using all the above mentioned polymer of PPy, PF and PTh have observed to quit same or a very
level of the theory. Optimized geometry and parameters (bond an- small difference has been observed.
gle and bond length) calculation was obtained by using DFT. Fre- The calculated bond angle of PPy, PF and PTh are totally differ-
quencies are assigned by using Gabedet. ent from each other as shown in Tables 4, 5, 6. The polymers hav-
The difference between HOMO and LUMO orbital’s energy es- ing large bond length show strong interaction. From bond length
timates the band gape. The negative of HOMO estimated the ion- calculation we can analyses that the specie having large bond an-
ization potential, while the negative of LUMO is electron affinity. gle has more ability of interaction. As PPy have bond angle in the
The difference between the HOMO and LUMO energies estimates range of 110ᴼ , PF have bond angle in the range of 107ᴼ , while PTh
the electronic properties (natural bond orbital analysis, Mullikan have bond length in the range of 91ᴼ . The PPy have large bond
charge analysis) and conductivity measurement (band gape).UV– angle then PF and PTh and thus –NH- site offers strong interaction
vis spectra of the PPY,PF and PTH are simulated at DFT using B3LYP then PF and PTh. On the basis of our calculated data (Tables 4, 5, 6)
basis set 6-31G(d,p) [31]. All the calculations were per- formed by the order of strong interaction on the basis of bond PPy ˃ PF ˃ PTh.
DFT level theory. The intermediate bond angle distance observed from monomer to
polymer has been very small. The PPy have intermediate bond dis-
3. Results and discussions tance in the range of 121, PF have 116 and PTh have 120 bond angle
intermediate distances. It means that the PF show more interaction
3.1. Optimized geometric parameter due to electronegative –O- heteroatom then –NH- in PPy and –S-
in PTh.
Optimization of geometries have been taken as the first task to
determine the effect of heteroatom on varies geometric parame-
ters (bond length, bond angle) of the polymers of PF, PPy, and PTh 3.2. Charge analysis
(n=1,…,9 ‘n’ represents number of repeating units). The geometry-
optimization was carried out at DFT B3LYP/6-31G∗∗ basis set on The charge transferring phenomena for PF, PPy and PTh
neutral form. The optimized geometric structures were given in are simulated by Natural Bonding Orbital (QNBO ) and Mulliken
Fig. 2 (bond length), 03 (bond angle) respectively. The optimized (QMULLIKEN ) charge analysis at B3LYP/6-31G (d, p) level of DFT.
geometrical parameters of PF, PPy, PTh are given in Tables 1, 2, These properties are basis set dependent; however if the same
3 (bond length) and Tables 4, 5, 6 (bond angle) respectively. It can level of theories is used for different structures [B3LYP/6-31G (d)
be seen from Tables 1, 2, 3 that when the number of ring increases or B3LYP/6-311++G (d, p)] [35] then the result will provide trend
the change in bond length occurs is quit smaller. However, by com- and there for be meaning full. The basis set dependence of these

3
A. Hassan, M. Ismail, A.H. Reshak et al. Journal of Molecular Structure 1274 (2023) 134484

Fig. 3. Optimized bong angle of PF(1), PTh(2) and PPy(3) where n=1...9 repeating units.

charge analysis tool has been discuss by Svantunek et al. [36] and 271 nm, λmax of PTh are observed at 308 nm and λmax of PPy are
B Han et al. [37]. observed at 254.88 nm when n=2. Three prominent peaks are ob-
The net charge distribution for heterocyclic polymers (PF, PTh, served in PTh, λmax are observed at 379.82 nm, four prominent
PPy) is quite different from each other, as shown in Table 7. The peaks are observed in UV–vis spectra of PF and PPy, λmax of PF
net charge distribution for 1PF is 1.338 based on Mullikan and are observed at 334.62 nm and that of PPy at 302 nm when n=3.
2.264 based on NBO, for 1PPy is 1.482 based on Milliken and 2.727 Four prominent peaks are observed in PF, λmax of PF are observed
based on NBO while for 1PTh is 1.445 based on Milliken and 2.93 at 383.81 nm, three prominent peaks are observed in PTh and in
based on NBO. By increasing the conjugated length the net charge PPy, λmax of PTh are observed at 437.29 nm and λmax of PPy ob-
distribution of PF, PPy [32], PTh will also increasing. For ring 9 the served at 341.47 when n=4. Three prominent peaks are observed in
net charge distribution for PF is 14.21 based on Milliken and 19.37 PF, λmax of PF observed at 423 nm, two prominent peaks are ob-
based on NBO, PPy is 16.838 based on Milliken and 20.882 based served in PPy and in PTh, λmax of PPy observed at 365 nm and in
on NBO, while PTh is 9.195 based on Mulliken and −18.378 based PTh at 482 nm when n=5. Four prominent peaks in UV–vis spec-
on NBO. From our theoretical data we conclude that the PTh show tra of PF are ob- served, λmax of PF observed at 454.37 nm, three
minimal net charge distribution from PPy and PF based on QNBO peaks are observed in UV–vis spectra of PTh and PPy, λmax of PTh
and QMULLIKEN , while PPy show maximal net charge distribution observed at 520.67 nm and in PPy at 383.47 nm when n=6. Four
both in NBO and Milliken. This because the oxygen is the most peaks in UV–vis spectra of PF are observed, λmax of PF observed
electro-negative and the Sulphur is the least electronegative of the at 49.68 nm and three peaks are observed in UV–vis spectra of
three heteroatoms. PPy and PTh, λmax of PPy ob- served at 398.30 nm and PTh at
535.88 nm when n=7. Four prominent peaks are ob- served in UV–
vis spectra of PF, λmax of PF observed at 500.18 nm while three
3.3. UV–vis spectroscopic study
peak are observed in UV–vis spectra of PTh and PPy, λmax of PTh
observed at 560.42 nm and in PPy at 408.93 nm when n=8. In
In UV–vis spectra the transition energies and oscillator strength
case of n=9 three prominent peaks are observed in PTh and PPy,
are stimulated by using B3LYP/6 31G (d, p) level of DFT method.
Calculated excitation energies, oscillator strength and molecular or-
λmax of PTh observed at 580.50 nm and in PPy at 417.80 nm, while
four prominent peaks are observed in UV–vis spectra of PF, λmax
bital of the first allowed singlet transitions for PPy, PF, PTh (n=
of PF are ob served at 479.68 nm. From the above discussion it
1…9 repeating units) are given in Tables 8, 9, 10.
is concluded that the different heteroatom’s (–O-, -NH- and –S-
Three prominent peaks are observed in UV–vis spectra of PTh
) in the rings produce comparable spectra as can be seen in the
λmax of which are observed at 209 nm (π → π ∗ ), two promi-
given Fig. 4. The absorption wavelength arising from So → S1 elec-
nent peaks are observed in UV–vis spectra of PF and in PPy, the
tronic transition increases progressively with the increasing of con-
λmax of PF are observed at 190 nm (π → π ∗ ) and in PPy λmax ob-
jugated chain length. Importantly the maximal absorption shows
served at 183 nm when n=1. Three prominent peaks are observed
a bathochromic shift when passes from small molecule to big one
in UV–vis spectra of PF, PPy and PTh, λmax of PF are observed at

4
A. Hassan, M. Ismail, A.H. Reshak et al. Journal of Molecular Structure 1274 (2023) 134484

Fig. 4. UV–vis spectrum of PPy, PF, and PTh from n=1...9.

5
A. Hassan, M. Ismail, A.H. Reshak et al. Journal of Molecular Structure 1274 (2023) 134484

Table 1 Table 2
(I, II, III): Optimized bond length of polyfuran (n=1, 2, 3, 4, 5, 6, 7, 8, 9), at (I, II, III): Optimized bond length of polypyrrole (n=1, 2, 3, 4, 5, 6, 7, 8, 9),
B3LYP/6-31G (d, p) level of theory. (Atomic labels of Table I, II, III are with using B3LYP/6-31G(d, p) level of theory. (Atomic labels are with reference
reference to Fig. 2. to Fig. 2).

I: n=1, 2, 3. I: n=1, 2, 3
# of rings with atoms 1PF 2PF 3PF Exp. # of rings with atoms 1PPy 2PPy 3PPy Exp.

I 1C-2O 1.3642 1.3652 1.36503 1.366 I 1C-2NH 1.3752 1.3747 1.3745 1.380
2O-3C 1.3642 1.3691 1.3697 2NH-3C 1.3752 1.3795 1.3801
II 1C-2O — 1.3691 1.3706 II 1C-2NH — 1.3795 1.3790
2O-3C — 1.3652 1.3706 2NH-3C — 1.3747 1.3790
IV 1C-2O — — 1.3697 II 1C-2NH — — 1.3801
2O-3C — — 1.3650 2NH-3C — — 1.3745
Intermediate distance (a…b)∗ — 1.43847 1.43538 Intermediate distance — 1.4494
∗
:, Intermediate bond distances between rings. (a…b)∗ 1.44747
∗
Exp: experimental data from reference [33]. : Intermediate bond distances between rings. Exp: experimental
data from reference 47.
II: n= 4, 5, 6,
# of rings with atoms 4PF 5PF 6PF II: n=4, 5, 6.
# of rings with atoms 4PPy 5PPy 6PPy
I 1C-2O 1.3650 1.43538 1.3649
2O-3C 1.3696 1.3697 1.3696 I 1C-2NH 1.3745 1.3744 1.3744
II 1C-2O 1.3703 1.3702 1.3701 2NH-3C 1.3801 1.3802 1.3801
2O-3C 1.3710 1.3713 1.3712 II 1C-2NH 1.3795 1.3787 1.3795
III 1C-2O 1.3710 1.3710 1.3709 2NH-3C 1.3804 1.3797 1.3805
2O-3C 1.3696 1.3710 1.3711 III 1C-2NH 1.3804 1.3795 1.3793
IV 1C-2O 1.3697 1.3713 1.3711 2NH-3C 1.3797 1.3795 1.3796
2O-3C 1.3651 1.3702 1.3709 IV 1C-2NH 1.3801 1.3797 1.3795
V 1C-2O — 1.3697 1.3712 2NH-3C 1.3751 1.3787 1.3794
2O-3C — 1.3650 1.3701 V 1C-2NH — 1.3802 1.3797
VI 1C-2O — — 1.3696 2NH-3C — 1.3743 1.3786
2O-3C — — 1.3649 VI 1C-2NH — — 1.3802
Intermediate distance (a…b)∗ 1.43144 1.43090 1.43052 2NH-3C — — 1.3743
∗
:, Intermediate bond distances between ring Intermediate distance
∗
(a…b) 1.44442 1.44434 1.44421
III: n=7, 8, 9 ∗
:, Intermediate bond distances between rings.
# of rings with atoms 7PF 8PF 9PF
III: n=7, 8, 9.
I 1C-2O 1.36500 1.3650 1.3650
# of rings with atoms 7PPy 8PPy 9PPy
2O-3C 1.3697 1.3697 1.3697
II 1C-2O 1.3703 1.3702 1.3702 I 1C-2NH 1.3744 1.3744 1.3743
2O-3C 1.3713 1.3714 1.3714 2NH-3C 1.3802 1.3802
III 1C-2O 1.3713 1.3709 1.3709 1.38021
2O-3C 1.3712 1.3713 1.3713 II 1C-2NH 1.3787 1.3787 1.3788
IV 1C-2O 1.3711 1.3711 1.3711 2NH-3C 1.3796 1.3797 1.3797
2O-3C 1.3711 1.3712 1.3712 III 1C-2NH 1.3804 1.3794 1.3803
V 1C-2O 1.3711 1.3712 1.3711 2NH-3C 1.3805 1.3795 1.3806
2O-3C 1.3709 1.3711 1.3711 IV 1C-2NH 1.3794 1.3805 1.3793
VI 1C-2O 1.3714 1.3713 1.3712 2NH-3C 1.3796 1.3795 1.3795
2O-3C 1.3702 1.3709 1.3711 V 1C-2NH 1.3796 1.3794 1.3805
VII 1C-2O 1.3697 1.3713 1.3713 2NH-3C 1.3794 1.3796 1.3804
2O-3C 1.3650 1.3702 1.3709 VI 1C-2NH 1.3797 1.3796 1.3795
VIII 1C-2O — 1.3697 1.3713 2NH-3C 1.3787 1.3794 1.3794
2O-3C — 1.3650 1.3702 VII 1C-2NH 1.3802 1.3797 1.3796
IX 1C-2O — — 1.3697 2NH-3C 1.3743 1.3787 1.3794
2O-3C — — 1.3650 VIII 1C-2NH — 1.3802 1.3797
Intermediate distance (a…b)∗ 1.43024 1.43010 1.4301 2NH-3C — 1.3743 1.3786
IX 1C-2NH — — 1.3802
∗
:, Intermediate bond distances between rings. 2NH-3C — — 1.3744
Intermediate distance
(a…b)∗ 1.44418 1.44396 1.44401
∗
:, Intermediate bond distances between rings
which also can be seen respectively from monomers of PPy, PF, and
PTh to 9 repeated units as can be seen from Table 8. From spec-
troscopic study of PF, PTh and PPy we conclude that the PTh show
maximum absorption as compared to PF and PPy. In view of ob- ized gradient approximation (GGA) is also an appropriate method
served and theoretically calculated UV–vis data it would be found for simulating the vibration spectra of a finite and infinite num-
that with increasing conjugation length the order of maximum ab- ber of atoms. H Ullah et al. [38] reported that GGA can success-
sorption is PTh ˃ PF ˃ PPy. fully predict the structural and vibrational properties of closed
and open-shell systems for oxides of actinide compounds. Further-
3.4. Vibrational spectra more, they correlated the reliability of GGA with CASPT2, which
is a highly computationally demanding method. Adjokatse et al.
The vibrational spectra of PPy, PF and PTh were calculated by [39] had also systematically studied the dielectric and piezoelec-
using B3LYP/6-31G (d, p) level of DFT method. The observed ma- tric response of odd-numbered nylons with the help of the DFT
jor band frequencies of PPy, PF, and PTH along with their rela- method with GGA and found nice correlation of the theoretically
tive intensities and probable vibration assignment are presented simulated vibrational spectrum with that of available experimen-
in Table 11. The theoretically calculated I.R spectra of PPy, PTh, tal data. For conducting polymers, literature reveals that pure GGA
and PF are plotted on Origin Pro 8.5 as shown in Fig. 5. General- and hybrid B3LYP are quite effective at simulating the vibrational

6
A. Hassan, M. Ismail, A.H. Reshak et al. Journal of Molecular Structure 1274 (2023) 134484

spectra; however, the latter is more abundantly used in the litera-

Table 3 ture [40].
(I, II, III): Optimized bond length of polythiophene (n=1, 2, 3, 4, 5, 6, 7, 8, 9), Vibrational spectroscopy is a key characterization for structural
using B3LYP/6-31G (d, p) level of theory. (Atomic labels are with reference to
elucidation.
Fig. 2).
The simulated scaled IR spectrum of 1PPy has major prominent
I: n=1, 2, 3 band peak at 461.26 cm−1 and has assigned twisting vibration,
# of rings with atoms 1PTh 2PTh 3PTh Exp
simulated scaled IR spectrum of 1PF has major prominent band
I 1C-2S 1.7357 1.7360 1.7360 1.752 peak at 759.54 cm−1 assigned wagging vibration, while simulated
2S-3C 1.7357 1.7569 1.7580
scaled IR spectrum of 1PTh has major prominent band peak at
II 1C-2S — 1.7569 1.7575
2S-3C — 1.7360 1.7575
729.6 cm−1 as- signed asymmetric stretching and ring deforma-
IV 1C-2S — — 1.7580 tion. The simulated scaled IR spectrum of 2PPy has major promi-
2S-3C — — 1.7580 nent band peak at 489.55 cm−1 assigned twisting vibration, the
Intermediate distance (a—b)∗ — 1.45061 1.44657 simulated scaled IR spectrum of 2PF has major prominent band
∗
: Intermediate bond distance between rings. Exp: experimental data [34].
peak at 733.75 cm−1 and also assigned twisting vibration like 2PPy,
II: n=4, 5, 6 while the simulated scaled IR spectrum of 2PTh has major promi-
# of rings with atoms 4PTh 5PTh 6PTh nent band peak at 681 cm−1 and assigned wagging vibration. The
I 1C-2S 1.7356 1.7353 1.7351 3PPy has major prominent band peak at 768.52 cm−1 and assigned
2S-3C 1.7577 1.7581 1.7580 wagging vibration, 3PF has major prominent peak at 1042 cm−1
II 1C-2S 1.7573 1.7575 1.7573 and assigned scissoring vibration, while 3PTh has major prominent
2S-3C 1.7582 1.7588 1.7587
peak at 696.5 cm−1 and assigned twisting vibration. The simu-
III 1C-2S 1.7582 1.7587 1.7586
2S-3C 1.7573 1.7587 1.7588 lated scaled IR major peak band spectrum of 4PPy as- signed scis-
IV 1C-2S 1.7577 1.7588 1.7587 soring vibration at 1105.01 cm−1 , 4PF assigned wagging vibration
2S-3C 1.7356 1.7575 1.7586 at799.36 cm−1 while 4PTh assigned wagging and ring deforma-
V 1C-2S — 1.7581 1.7588 tion at 701.2 cm−1 . The simulated scaled IR major peak band spec-
2S-3C — 1.7353 1.7573
VI 1C-2S — — 1.7580
trum of 5PPy assigned wagging vibration at 785.78 cm−1 , 5PF as-
2S-3C — — 1.7352 signed scissoring vibration at 1043.23 cm−1 while 5PTh assigned
Intermediate distance (a…b)∗ 1.44214 1.44165 1.44092 asymmetric stretching at 688.3 cm−1 . The major prominent IR peak
band simulated for 6PPy at 782.67 cm−1 assigned wagging vibra-
∗
:, Intermediate bond distances between rings

III: n=7, 8, 9
tion, for 6PF at 810.49 cm−1 assigned twisting vibration, for PTh
# of rings with atoms 7PTh 8PTh 9PTh at1547.9 cm−1 assigned asymmetric stretching vibration. The major
peak band of IR simulated for 7PPy at1562.25 cm−1 assigned asym-
I 1C-2S 1.735 1.735 1.735
2S-3C 1.7572 1.7572 1.7572 metric stretching and ring deformation, for 7PF at 810.49 cm−1 as-
II 1C-2S 1.7564 1.7564 1.7564 signed twisting vibration, for 7PTh at 1572.02 cm−1 assigned asym-
2S-3C 1.7577 1.7577 1.7577 metric stretching and ring deformation. The simulated scaled IR
III 1C-2S 1.7578 1.7577 1.7577
major peak band for 8PPy at 768.81 cm−1 assigned wagging vi-
2S-3C 1.7581 1.7582 1.7581
IV 1C-2S 1.7581 1.7581 1.758
bration, for 8PF at 1552.63 cm−1 assigned asymmetric stretching
2S-3C 1.7581 1.7582 1.7582 vibration, for 8PTh at 1555 cm−1 also assigned asymmetric stretch-
V 1C-2S 1.7581 1.7582 1.7582 ing vibration. The simulated scaled IR spectrum of 9PPy has major
2S-3C 1.7578 1.7581 1.7582 prominent band peak at 762.60 cm−1 and assigned wag- ging, sim-
VI 1C-2S 1.7578 1.7582 1.7582
ulated scaled IR spectrum of 9PF has major prominent band peak
2S-3C 1.7564 1.7577 1.758
VII 1C-2S 1.7572 1.7577 1.7581 at 1553.53 cm−1 assigned asymmetric stretching vibration while
2S-3C 1.735 1.7564 1.7577 simulated scaled IR spectrum of 9PTh has major band peak at
VIII 1C-2S — 1.7572 1.7577 1563.1 cm−1 and assigned asymmetric stretching vibration.
2S-3C — 1.735 1.7564
IX 1C-2S — — 1.7572
2S-3C — — 1.735 3.5. HOMO LUMO energy gap
Intermediate distance (a…b)∗ 1.44161 1.44135 1.4413
∗
:, Intermediate bond distances between rings
The HOMO and LUMO energy of polypyrrole (PPy), polyfuran
(PF) and polythiophene (PTh) calculated at B3LYP/6-31G (d, p) level
of DFT. The HOMO and LUMO energy give information about elec-
tronic properties such as ionization potential (I.P), electron affin-
ity (E.A) and energy gap. "range-separated functionals estimates
HOMO–LUMO gaps and excited-state energies better" [41–44]. The

Table 4
Optimized bond angle of polythiophene (n=1, 2, 3, 4, 5, 6, 7, 8, 9), using B3LYP/6-31G∗ ∗ level of theory (Atomic labels are with reference to Fig. 3).

Spe- cies 1 1C-2S-3C II 1C-2S-3C III 1C-2S-3C IV 1C-2S-3C V 1C-2S-3C VI 1C-2S-3C VII 1C-2S-3C VIII 1C-2S-3C IX 1C-2S-3C a…b…c∗

1PTh 91.51 —– —– —– —– —– —– —– —– —–
2PTh 91.83 91.83 —– —– —– —– —– —– —– 120.93
3PTh 91.78 92.17 91.79 —– —– —– —– —– —– 120.79
4PTh 91.80 92.17 92.17 91.80 —– —– —– —– —– 120.85
5PTh 91.77 92.14 92.13 92.15 91.77 —– —– —– —– 120.79
6PTh 91.78 92.14 92.12 92.12 92.14 91.78 —– —– —– 120.82
7PTh 91.76 92.10 92.09 92.09 92.09 92.10 91.76 —– —– 120.78
8PTh 91.75 92.10 92.09 92.09 92.09 92.09 92.10 91.76 —– 120.79
9PTh 91.75 92.10 92.09 92.09 92.09 92.09 92.09 92.10 91.76 120.80
∗
:, an intermediate bond distances between rings.

7
A. Hassan, M. Ismail, A.H. Reshak et al. Journal of Molecular Structure 1274 (2023) 134484

Table 5
Optimized bond angle (ᴼ ) of polyfuran (n=1, 2, 3, 4, 5, 6, 7, 8, 9), using B3LYP/6-31G∗ ∗ level of theory (Atomic labels are with reference to Fig. 3).

Spe- cies I 1C-2O-3C II 1C-2O-3C III 1C-2O-3C IV 1C-2O-3C V 1C-2O- 3C VI 1C-2O- 3C VII 1C-2O-3C VIII 1C-2O-3C IX 1C-2O-3C a….b…c∗

1PF 106.77 —– —– —– —– —– —– —– —– —–
2PF 106.94 106.94 —– —– —– —– —— —– —– 116.68
3PF 106.94 107.09 106.93 —– —– —– —– —– —– 116.75
4PF 106.89 107.08 107.08 106.89 —– —– —– —– —– 116.72
5PF 106.90 107.07 107.08 107.07 106.9 0 —– —– —– —– 116.74
6PF 106.89 107.06 107.068 82 107.06 107.0 6 106.8 9 —– —– —– 116.76
7PF 106.90 107.07 107.08 107.07 107.0 8 107.0 7 106.90 —– —– 116.79
8PF 106.90 107.07 107.08 107.07 107.0 7 107.0 8 107.07 106.90 —– 116.78
9PF 106.90 107.07 107.08 107.07 107.0 8 107.0 7 107.08 107.07 106.90 116.76
∗
:, Intermediate bond distances between rings.

Table 6
Optimized bond angle of polypyrrole (n=1, 2, 3, 4, 5, 6, 7, 8, 9), using B3LYP/6-31G∗ ∗ level of theory (Atomic labels are with reference to Fig. 3).

Spe cies I 1C-2NH-3C II 1C-2NH-3C III 1C-2NH-3C IV 1C-2NH-3C V 1C-2NH-3C VI 1C-2NH- 3C VII 1C-2NH-3C VIII 1C-2NH-3C IX 1C-2NH-3C a...b…c∗

1PPy 109.80 —– —– —– —– —– —– —– —– —–
2PPy 110.23 110.2 3 —– —– —– —– —– —– —– 121.51
3PPy 110.22 110.7 7 110.22 —– —– —– —– —– —– 121.71
4PPy 110.20 110.6 3 110.63 110.20 —– —– —– —– —– 121.63
5PPy 110.21 110.7 8 110.79 110.78 110.21 —– —– —– —– 121.76
6PPy 110.19 110.6 4 110.76 110.77 110.77 110.21 —– —– —– 121.80
7PPy 110.21 110.7 5 110.62 110.76 110.78 110.78 110.21 —– —– 121.77
8PPy 110.21 110.7 7 110.75 110.63 110.75 110.77 110.77 110.21 —– 121.61
9PPy 110.21 110.7 5 110.63 110.72 110.61 110.76 110.77 110.77 110.207 32 121.62
Exp. 11.82
∗
:, an intermediate bond distances between rings. Exp.: experimental values.

Table 7
NBO and Mulliken charge distribution calculation of PPy, PF, PTh where n= 1….9 repeating units
at B3LYP/6-31G (d, p) level of DFT.

# of Ring Species QMullikan QNBO

I 1PF 1.338 2.264

1PPy 1.482 2.727
1PTh 1.445 2.93
II 2PF 0.03 0.122
2PPy 0.602 0.15
2PTh 0.105 0,745
III 3PF 4.556 6.422
3PPy 5.368 7.196
3PTh 3.351 6.788
IV 4PF −0.027 0.884
4PPy 0.0098 0.017
4PTh 0.109 252.89
V 5PF 7.773 10.562
5PPy 9.323 10.64
5PTh 5.326 10.406
VI 6PF −1.318 4.765
6PPy 11.506 12.780
6PTh −0.195 452.40
VII 7PF 10.501 14.349
7PPy 13.248 16.342
7PTh 6.805 14.346
VIII 8PF 12.604 16.44
8PPy 15.217 18.611
8PTh 8.258 16.53
IX 9PF 14.21 19.376
9PPy 16.838 20.882
9PTh 9.195 -18.378

8
A. Hassan, M. Ismail, A.H. Reshak et al. Journal of Molecular Structure 1274 (2023) 134484

Fig. 5. Scaled Infrared spectrums of PF, PPy and PTh from n=1...9.

HOMO and LUMO diagram of PPy, PF and PTh are given in Figs. Table 12. The energy gap obtained from the difference between
6 and 7. The HOMO and LUMO of PPy (n=1……9) are extended HOMO and LUMO. The HOMO, LUMO energy difference of PPy in
to all Carbons, hydrogen and nitrogen’s (- NH-) and form a ladder the range of 3.44 eV, 2.78 eV for PF, while for PTh in the range of
like structure and involve delocalization over the entire molecule 2.49 eV. It can be concluded from the result that PTh show low en-
framework. Similarly for PF (n= 1……9) are extended to all car- ergy gap as compared to PF and PPy. The low energy gap the more
bons and oxygen (-O-) and ladder like structure formed and in- will be conductivity. So PTh is more conductive as compared to PF,
volve delocalization over the entire molecule framework, while in PPy, and strongest candidates for forming material conductive. The
PTh (n= 1… 9), the HOMO and LUMO are extended to all carbons conductivity range according to the calculated data is PTh ˃ PF ˃
and sulphur (-S-) and form a ladder like structure and involve de- PPy.
localization over the entire molecule framework. The HOMO and
LUMO energies and associated energy gap of the PPy, PF and
PTh from monomers up to polymers repeating units are given in

9
A. Hassan, M. Ismail, A.H. Reshak et al. Journal of Molecular Structure 1274 (2023) 134484

Fig. 6. Plot of the calculated Energy band gap ࢞E of PTh, PF, PPy against the reciprocal of corresponding oligomers length, i.e, the number of monomers units.

Table 8
Calculated Excitation Energies, Oscillator Strengths, and Molecular Orbit- als (MOs) of the First Allowed Singlet Transition
Involved in the Excitation for PF, Where n = 1…9 at B3LYP/6- 31G (d, p) Level of Theory.

Species MOs Energy (eV) Wavelength (nm) Oscillator Strength Exp O.S

1PF 18→19 6.4988 190.78 0.1440

2PF 35→36 4.5646 271.62 0.5772
3PF 52→53 3.7052 334.62 0.8517
4PF 69→70 3.2304 383.81 1.2074 1.30
5PF 86→87 2.9310 423.01 1.5309 1.66
6PF 103→104 2.7287 454.37 1.8474 2.00
7PF 120→121 2.5847 479.68 2.1474 2.32
8PF 137→138 2.4788 500.18 2.4434
9PF 154→155 2.3992 516.78 2.7342

Exp O.S: experimental values of oscillator strength

Table 9 Table 11
Calculated Excitation Energies, Oscillator Strengths, and Molecular Orbital’s (MOs) Comparison of theoretically calculated IR intensities, Frequency, Mode number and
of the First Allowed Singlet Transition Involved in the Excitation for PPy, Where vibrational assignment of PPy, PF and PTh (n= 1…9), using B3LYP/6- 31G (d, p) level
n = 1…9 at B3LYP/6- 31G (d, p) Level of Theory. of theory.
Species MOs Energy (eV) Wavelength (nm) Oscillator Strength Ring # Specie Mode # Frequency IR Intensi- ty Vibration
1PPy 18→19 6.7415 183.91 0.1439 I 1PPy 1 461.26 77.43 γ.
2PPy 35→36 4.8645 254.88 0.5512 1PF 4 759.44 77.6380 Wagg
3PPY 52→53 4.1046 302.06 0.8492 1PTh 5 729.6 102.6 ν as , Def(ring)
4PPy 69→70 3.6309 341.47 1.1963 II 2PPy 8 489.59 18.959 
5PPy 86→87 3.3964 365.05 1.5015 2PF 11 733.75 72.1388 
6PPy 103→104 3.2333 383.47 1.7975 2PTh 12 681.0 0.000 Wagg
7PPy 120→121 3.1128 398.30 2.0856 III 3PPy 24 768.52 114.35 Wagg
8PPy 137→138 3.0319 408.93 2.3894 3PF 35 1042.00 10.1922 B
9PPy 154→155 2.9676 417.80 2.6879 3PTh 23 696.5 106.5 
IV 4PPy 55 1105.01 119.5703 B
4PF 29 799.36 105.412 Wagg
4PTh 32 701.2 0.0000 Wagg, Def (ring)
V 5PPy 45 785.78 28.8778 Wagg
5PF 61 1043.23 3.3831 B
Table 10 5PTh 38 688.3 0.0152 ν as
Calculated Excitation Energies, Oscillator Strengths, and Molecular Orbital’s (MOs) VI 6PPy 51 762.87 48.1890 Wagg
of the First Allowed Singlet Transition Involved in the Excitation for PTh, Where 6PF 50 810.49 0.0002 
n = 1…9 at B3LYP/6- 31G (d, p) Level of Theory. 6PTh 107 1547.9 339.5 ν as , Def (ring)
VII 7PPy 138 1562.25 0.8400 ν as , Def (ring)
Species MOs Energy (eV) Wavelength (nm) Oscillator Strength 7PF 59 810.41 18.70 
1PTh 22→23 5.9207 209.41 0.0873 7PTh 127 1572.02 0.6692 ν as , Def (ring)
2PTh 43→44 4.0235 308.15 0.4288 VIII 8PPy 74 768.81 4.4737 Wagg
3PTh 64→65 3.2643 379.82 0.8113 8PF 141 1552.63 367.55 ν as
4PTh 85→86 2.8353 437.29 1.2159 8PTh 144 1555.0 1.235 ν as
5PTh 106→107 2.5677 482.86 1.6051 IX 9PPy 78 762.60 48.0833 Wagg
6PTh 127→128 0.3812 520.67 1.9814 9PF 159 1553.53 504.88 ν as
7PTh 148→149 2.3136 535.88 2.3128 9PTh 163 1563.1 7.403 ν as
8PTh 169→170 2.2123 560.42 2.6563 β : Scissoring, ν as : Asymmetric stretching, Wagg: wagging, Def: ring deformation,
9PTh 190→191 2.1358 580.50 2.9925 γ : Twisting are predominated terms used/listed in the table.

10
A. Hassan, M. Ismail, A.H. Reshak et al. Journal of Molecular Structure 1274 (2023) 134484

Fig. 7. Frontier molecular orbital of PPy, PF and PTh, where n=1...9.

11
A. Hassan, M. Ismail, A.H. Reshak et al. Journal of Molecular Structure 1274 (2023) 134484

Table 12 Declaration of Competing Interest

HOMO, LUMO and band gap calculation for PPy, PF, PTh where n= 1…9
at B3LYP/6-31G (d, p) level of DFT.
The authors declare that they have no known competing finan-
# Of Rings Specie LUMO e V
HOMO eV Energy gap(࢞E) cial interests or personal relationships that could have appeared to
I 1PF 0.5053 6.1225 5.617 influence the work reported in this paper.
1PPy 1.3461 5.5037 4.158
1PTh −0.2291 6.3486 6.577 Data availability
II 2PF −0.6122 5.2683 5.881
2PPy 0.3232 4.7628 4.439
No data was used for the research described in the article.
2PTH −1.2626 5.4863 6.749
III 3PF −1.0707 4.9184 5.989 References
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