See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/351836218

Orientation dependent DFT analysis of aniline and pyrrole based copolymer

Article  in  Materials Today: Proceedings · May 2021

DOI: 10.1016/j.matpr.2021.05.193

CITATIONS READS

0 28

5 authors, including:

Kirtesh Pratap Khare Reena Srivastava

Amity University Jiwaji University
6 PUBLICATIONS   0 CITATIONS    17 PUBLICATIONS   35 CITATIONS   

SEE PROFILE SEE PROFILE

Anurag Srivastava
ABV-Indian Institute of Information Technology and Management Gwalior
230 PUBLICATIONS   1,418 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

CNT and GRAPHENE based Sensor View project

Gas/Chemical and Bio Sensors using 1D and 2D nano materials View project

All content following this page was uploaded by Kirtesh Pratap Khare on 02 June 2021.

The user has requested enhancement of the downloaded file.

 Materials Today: Proceedings xxx (xxxx) xxx

Contents lists available at ScienceDirect

Materials Today: Proceedings

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

Orientation dependent DFT analysis of aniline and pyrrole based

copolymer
Kirtesh Pratap Khare a,b,⇑, Rachana Kathal a, Neelima Shukla c, Reena Srivastava b,d, Anurag Srivastava b
a
Dept. of Chemistry, Amity School of Engineering & Technology, Amity University Madhya Pradesh, Maharajpura Dang, Gwalior, (MP) 474005, India
b
Advanced Materials Research Group, CNT Lab, ABV-Indian Institute of Information Technology and Management, Gwalior, (M.P.) 474015, India
c
Dept. of Chemistry, S.M.S Government Model Science College, Gwalior, (M.P.) 474002, India
d
Dept. of Chemistry, Government S L P College, Morar, Gwalior, (M.P.) 474001, India

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

Article history: Conducting polymers (CPs) are very important materials owing to their large surface area, high thermal
Received 30 June 2020 stability, good conductivity, moldability, and easy process modifications to govern their properties.
Received in revised form 17 March 2021 Polymers that remarkably conduct electricity have bestowed mankind with the field of organic electron-
Accepted 6 May 2021
ics. Few polymers have emerged as potential candidates for the trace level detection of anticancer drugs.
Available online xxxx
The present work explores the electronic properties and stability of poly-aniline (Ani-Ani), poly-pyrrole
(Py-Py), and their copolymer (Ani-Py) at different orientations, investigated using density functional the-
Keywords:
ory (DFT) based approach. A comparative analysis of electronic properties of aniline-pyrrole copolymer
DFT
Poly-aniline
with its host polymers with varied orientation show reduced HOMO-LUMO gap, variation in density of
Poly-pyrrole state (DOS) profile and the binding energy as a function of orientation of molecule. It is observed that
Copolymer copolymerization enhances the designing capability of electrochemical polymeric sensors for detection,
HOMO-LUMO quantification, determination and validation of anti-cancer drugs in comparison to the sensors based on
DOS poly-aniline and poly-pyrrole polymers.
Ó 2021 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Confer-
ence on Advances in Design, Materials and Manufacturing.

1. Introduction such conducting polymers, poly-aniline (Ani-Ani) and poly-

Conducting polymers (CPs) afford chemical stability and tun-
able conductivity range between metal and insulator. Conducting
polymers are the organic materials that conduct electricity due
to the presence of delocalized p electrons. Such compounds may
either have semiconductor or metallic conductivity [1,2]. Discov-
ery of polymers has given a new dimension to recent electronics.
Earlier, polymers were considered resource for heat sensitive, flex-
ible, electrically insulating amorphous materials. Electrically Con-
ducting polymers have been studied a lot by the experimental
[3–9] as well as theoreticians [10–12] appear to be ideal candidates
for various applications such as photoactive materials, electro
chromic display materials, sensors, electro active materials, light-
emitting diodes, artificial muscles and solar cell materials. Two
⇑ Corresponding author at: Dept. of Chemistry, Amity School of Engineering &
Technology, Amity University Madhya Pradesh, Maharajpura Dang, Gwalior, (M.P.)
474005, India.
E-mail address: kirteshkhare01@gmail.com (K. Pratap Khare).
pyrrole (Py-Py) have been reported in literature by theoretical
[13] as well as experimental [14,15] researchers for their charac-
teristic, possible applications and their efficient synthetic mea-
sures as well. In the present work, the periodic structures of
poly-aniline and poly-pyrrole are worked out for their stability
and electronic properties using density functional theory (DFT).
As the physical, electronic and mechanical properties of conduct-
ing polymers can be reframed by copolymerization [16], same
studies have also been carried out for the modeled aniline-
pyrrole copolymer at different orientations, and the effects of
copolymerization on the stabilities and electronic properties [17–
21] of the poly-aniline and poly-pyrrole polymers have been anal-
ysed in terms of molecular energy spectrum and density of states.
2. Computational details
Electronic and structural properties of poly-aniline, poly-
pyrrole and their copolymer (Ani-Py) have been computed using
generalized gradient approximation (GGA), parameterized with

https://doi.org/10.1016/j.matpr.2021.05.193
2214-7853/Ó 2021 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Conference on Advances in Design, Materials and Manufacturing.

Please cite this article as: K. Pratap Khare, R. Kathal, N. Shukla et al., Orientation dependent DFT analysis of aniline and pyrrole based copolymer, Materials
Today: Proceedings, https://doi.org/10.1016/j.matpr.2021.05.193
K. Pratap Khare, R. Kathal, N. Shukla et al. Materials Today: Proceedings xxx (xxxx) xxx

Fig. 1. Optimized geometries of poly-aniline (a), poly-pyrrole (b) and their copolymer orientations (c-h)

Perdew-Burke Ernezherof (PBE) type exchange correlation function
[22,23]. Controls have been performed using Atomistix Toolkit Vir-
tual Nano lab (ATK-VNL) environment, a density functional theory
(DFT) [24] based ab initio approach. ATK-VNL is a further advance-
ment of Trans SIESTA employing basis sets as developed in SIESTA.
Double zeta double polarized basis (DZDP) sets are used for core
and valence electronic states. A mesh cutoff of 75 Rydberg and
force tolerance of 0.05 was found suitable for the convergence.
The poly-aniline containing 12 carbon, 12 hydrogen and 2 nitro-
gen atoms, and poly-pyrrole contain 8 carbon, 8 hydrogen and 2
nitrogen atoms and their copolymer in all orientations contain 10
carbon, 10 hydrogen and 2 nitrogen atoms. Copolymer (Ani-Py)
at different orientations has been modeled and optimized geome-
tries are reported in Fig. 1, simulated to analyze its structural sta-
bility and electronic properties.
3. Results and discussion
3.1. Stability analysis
poly-pyrrole polymers confirms that the poly-aniline polymer is
having better stability in comparison to poly-pyrrole polymer,
however their modeled and optimized copolymer at orientation
2 in comparison to other orientations, has even better stability
than its host polymers.
3.2. HOMO-LUMO analysis
The optimized geometries of poly-aniline, poly-pyrrole and
their copolymer at different orientations have been analyzed for
their electronic properties in polymeric as well as copolymer form,
reported in Fig. 2. Where, the molecular energy spectrums of poly-
aniline and poly-pyrrole have also been computed and compared
with those of the copolymer at different orientations, reported in
Table 2. The computed HOMO-LUMO gap of poly-aniline is
3.9 eV and that of poly-pyrrole is 3.76 eV, however, the gap
decreases when they form copolymer at orientation 2 with a gap
of 3.2 eV. This can also be visualized through the density of state
profiles of these polymers as well as copolymers.

The optimized geometries of poly-aniline, poly-pyrrole and

their copolymer at different orientations, shown in Fig. 1, analyzed
4. Conclusion
for their stability are conferred in terms of their total energy,
reported in Table 1. The computed energy of poly-aniline and
The present work reports that the computational synthesis of a
copolymer of poly-aniline and poly-pyrrole polymers at different
orientations have successfully been performed by analysing their
Table 1
stability, electronic and structural properties, investigated using
Total energies of aniline, pyrrole and copolymer orientations (Refer Fig. 1). density functional theory (DFT) based ab-initio approach. The elec-
tronic properties have been analysed at different orientations in
System Total energy (eV)
terms of molecular energy spectrum, HOMO-LUMO and DOS pro-
Poly-aniline (a) 2621.956 file, reports the expected modulation in HOMO-LUMO gap of
Poly-pyrrole (b) 1929.042
Copolymer_or1 (c) 2274.829
copolymer (Ani-Py) at orientation 2 as compared to its host poly-
Copolymer_or2 (d) 2276.260 aniline and poly-pyrrole polymers. Hence, in view of the better sta-
Copolymer_or3 (e) 2276.108 bility and other computed properties it can be concluded that the
Copolymer_or4 (f) 2275.651 computationally synthesized copolymer (Ani-Py) at specific orien-
Copolymer_or5 (g) 2275.945
tation may be a better choice for anti-cancer drug polymeric sen-
Copolymer_or6 (h) 2276.174
sor, however, needs validation through laboratory experiment.
2
K. Pratap Khare, R. Kathal, N. Shukla et al. Materials Today: Proceedings xxx (xxxx) xxx

Fig. 2. HOMO-LUMO and DOS analysis of poly-aniline (a), poly-pyrrole (b) and copolymer orientations (c-h).

Table 2
HOMO-LUMO gap of poly-aniline, poly-pyrrole and copolymer orientations (Refer CRediT authorship contribution statement
Fig. 1 for defining orientations, Fig. 2 for respective HOMO-LUMO gap analysis).

System HOMO-LUMO gap (eV) Kirtesh Pratap Khare, Rachana Kathal and Anurag Srivastava
Poly-aniline (a)Poly-pyrrole (b) 3.9 have conceived of the presented idea. Kirtesh Pratap Khare and
3.76 Reena Srivastava have developed the theory and performed the
Copolymer_or1 (c) 4.02 computations. Neelima Shukla and Anurag Srivastava encouraged
Copolymer_or2 (d) 3.2 Kirtesh Pratap Khare to investigate the polymers and Anurag
Copolymer_or3 (e) 3.54
Srivastava, Rachana Kathal and Neelima Shukla supervised the
Copolymer_or4 (f) 3.2
Copolymer_or5 (g) 3.74 findings of this work. All authors discussed the results and con-
Copolymer_or6 (h) 3.6 tributed to the final manuscript.

3
K. Pratap Khare, R. Kathal, N. Shukla et al.
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.
Acknowledgements
The authors are extremely thankful to Atal Bihari Vajpayee,
Indian Institute of Information Technology and Management, Gwa-
lior (ABV-IIITM) for providing the Computational infrastructure of
AMR Group, to carry out the present research work.
References
[1] R. Kumar, R.P. Chauhan, R. Kumar, S.K. Chakarvarti, Synthesis of conducting
polymers and their characterization, (2010).
[2] S.C. Raghavendra, S. Khasim, M. Revanasiddappa, M.V.N.A. Prasad, A.B.
Kulkarni, Synthesis, characterization and low frequency ac conduction of
polyaniline/fly ash composites, Bull. Mater. Sci. 26 (2003) 733–739.
[3] N. Maragani, K. Vijaya Kumar, Structural and A.C. Conductivity studies of (PAN
+NaF) gel polymer electrolyte system with ZrO2nano filler for an
electrochemical cell applications, Rasayan J. Chem. 10 (2017) 1218–1225,
https://doi.org/10.7324/RJC.2017.1041723.
[4] Z. He, B. Xiao, F. Liu, H. Wu, Y. Yang, S. Xiao, C. Wang, T.P. Russell, Y. Cao, Single-
junction polymer solar cells with high efficiency and photovoltage, Nat.
Photon. 9 (2015) 174–179.
[5] A.L. Dyer, E.J. Thompson, J.R. Reynolds, Completing the color palette with
spray-processable polymer electrochromics, ACS Appl. Mater. Interfaces 3
(2011) 1787–1795.
[6] K. Dunst, J. Karczewski, P. Jasiński, Nitrogen dioxide sensing properties of
PEDOT polymer films, Sensors Actuators B Chem. 247 (2017) 108–113.
[7] D. Vonlanthen, P. Lazarev, K.A. See, F. Wudl, A.J. Heeger, A stable polyaniline-
benzoquinone-hydroquinone supercapacitor, Adv. Mater. 26 (2014) 5095–
5100.
[8] L. Pan, G. Yu, D. Zhai, H.R. Lee, W. Zhao, N. Liu, H. Wang, B.-C.-K. Tee, Y. Shi, Y.
Cui, Hierarchical nanostructured conducting polymer hydrogel with high
electrochemical activity, Proc. Natl. Acad. Sci. 109 (2012) 9287–9292.
[9] D. Yue, P. Khatav, F. You, S.B. Darling, Deciphering the uncertainties in life cycle
energy and environmental analysis of organic photovoltaics, Energy Environ.
Sci. 5 (2012) 9163–9172.
View publication stats
Materials Today: Proceedings xxx (xxxx) xxx
[10] F.C. Franco, Interaction of several toxic heterocarbonyl gases with polypyrrole
as a potential gas sensor, Chemosensors 8 (2020), https://doi.org/10.3390/
CHEMOSENSORS8030084.
[11] V. Picchio, V. Cammisotto, F. Pagano, R. Carnevale, I. Chimenti, We are
IntechOpen, the world ’ s leading publisher of Open Access books Built by
scientists, for scientists TOP 1 %, Intechopen (2020) 1–15. https://www.
intechopen.com/books/advanced-biometric-technologies/liveness-detection-
in-biometrics.
[12] H. Azak, R. Gorgul, B. Tekin, M. Yildiz, Calculation of conductive polymer-based
SO2 and SO3 gas sensor mechanisms by using the DFT method, J. Mol. Model.
25 (2019) 2–9, https://doi.org/10.1007/s00894-019-4219-9.
[13] M. Sardari, F.K. Fotooh, M.R. Nateghi, A DFT study of the structural and
electronic properties of periodic forms of aniline and pyrrole polymers and
aniline–pyrrole copolymer, J. Mol. Model. 24 (2018) 1–10.
[14] J. Vivekanandan, A. Mahudeswaran, X.-Y. Tang, S.G. Kumbar, P.S. Vijayanand,
Synthesis, characterisation, and electrical properties of novel nanostructured
conducting poly (aniline-co-m-chloroaniline) with incorporated silver
particles, Chem. Pap. 69 (2015) 964–972.
[15] A. Yussuf, M. Al-Saleh, S. Al-Enezi, G. Abraham, Synthesis and characterization
of conductive polypyrrole: the influence of the oxidants and monomer on the
electrical, thermal, and morphological properties, Int. J. Polym. Sci. 2018
(2018).
[16] M. Biswas, A. Roy, Thermal stability, morphological, dielectric, and
conductivity characteristics of pyrrole modified poly-N-vinyl carbazole, J.
Appl. Polym. Sci. 49 (1993) 2189–2196, https://doi.org/10.1002/app.1993.
070491215.
[17] K. Dutta, P. Kanjilal, R. Das, S. Thayumanavan, Synergistic interplay of covalent
and non-covalent interactions in reactive polymer nanoassembly facilitates
intracellular delivery of antibodies, Angew. Chemie Int. Ed. (2020).
[18] W.B. Liechty, D.R. Kryscio, B.V. Slaughter, N.A. Peppas, Polymers for drug
delivery systems, Annu. Rev. Chem. Biomol. Eng. 1 (2010) 149–173.
[19] A.A. Moghanjoughi, D. Khoshnevis, A. Zarrabi, A concise review on smart
polymers for controlled drug release, Drug Deliv. Transl. Res. 6 (2016) 333–
340.
[20] R. Srivastava, H. Suman, S. Shrivastava, A. Srivastava, DFT analysis of pristine
and functionalized Zigzag CNT: a case of H2S sensing, Chem. Phys. Lett. 731
(2019) 136575.
[21] M. Srivastava, A. Srivastava, S.K. Pandey, Suitability of graphene monolayer as
sensor for carcinogenic heavy metals in water: a DFT investigation, Appl. Surf.
Sci. 517 (2020) 146021.
[22] J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made
simple, Phys. Rev. Lett. 77 (1996) 3865.
[23] Y. Zhang, W. Yang, Comment on ‘‘Generalized gradient approximation made
simple”, Phys. Rev. Lett. 80 (1998) 890.
[24] E. Engel, R.M. Dreizler, Density Functional Theory, Springer, 2013.