Article

pubs.acs.org/JPCC

Doping and Dedoping Processes of Polypyrrole: DFT Study with

Hybrid Functionals
Habib Ullah, Anwar-ul-Haq Ali Shah,*, Salma Bilal, and Khurshid Ayub*,,

Institute of Chemical Sciences and National Centre of Excellence in Physical Chemistry, University of Peshawar, 25120 Peshawar,
Pakistan

Department of Chemistry, COMSATS Institute of Information Technology, University Road, Tobe Camp, 22060 Abbottabad,
Pakistan

Department of Chemistry, College of Science, King Faisal University, Al-Hafouf 31982, Saudi Arabia
S Supporting Information
*

ABSTRACT: Density functional theory (DFT) and time-dependent

DFT (TD-DFT) calculations at the UB3LYP/6-31G(d) level have been
performed to investigate the tunable nature, i.e., doping and dedoping
processes, of polypyrrole (PPy). The calculated theoretical data show
strong correlation with the recent experimental reports, which validates
our computational protocol. The calculated properties are extrapolated
to the polymer (PPy) through a second-order polynomial t. Changes in
band gap, conductivity, and resistance of nPy and nPy-X (where n = 19
and X = +, NH3, and Cl) were studied and correlated with the calculated
vibrational spectra (IR) and electronic properties. Upon doping, bridging
bond distance and internal bond angles decrease (decrease in resistance
over polymer backbone), whereas dedoping results in increases in these
geometric parameters. In the vibrational spectrum, doping is
characterized by an increase in the band peaks in the ngerprint region and/or red shifting of the spectral bands. Dedoping
(9Py+ with NH3), on the other hand, results in decreases in the number of vibrational spectral bands. In the UVvis and UV
visnear-IR spectra, the addition of dierent analytes (dopant) to 9Py results in the disappearance of certain bands and gives rise
to some new absorbances corresponding to localized and delocalized polaron bands. Specically, the peaks in the near-IR region
at 1907 nm for Py+ and 1242 nm for 9Py-Cl are due to delocalized and localized polaron structures, respectively. Upon p-doping,
the band gaps and resistance of nPy decrease, while its conductivity and -electron density of conjugation increase over the
polymeric backbone. However, a reversal of properties is obtained in n-doping or reduction of nPy+. In the case of oxidation and
Cl dopant, the IP and EA increase, and consequently, there is a decrease in the band gap. NBO and Mulliken charges analyses
indicate charge transferring from the polymer in the case of p-type dopants, while this phenomenon is reversed with n-type
dopants.

1. INTRODUCTION

conduct electricity in the presence of a dopant (iodine). PPy

is physically insoluble, amorphous, and infusible.
PPy has been extensively studied both experimentally and
theoretically for applications as sensors, actuators, and
corrosion inhibitors. Recently, we have also carried out a
theoretical study to investigate its ability as a sensor for NH3
gas in its undoped form.5 A large number of papers have been
published on experimental studies of PPy as sensor for
methanol, ethanol, NO2, NH3, CO2, and CO and other toxic
gases.1518 For improved performance (high crystallinity and
conductance), PPy is modied with some coating material such
as TiO2 or ZnO.19 Moreover, to enhance the performance of
PPy, dierent approaches have been reported, such as
minimizing the band gap, composites,20 and nano studies.21

Conjugated organic polymers (COPs) are technologically

important,1 due to their tunable nature,2 free availability of electrons on the backbone of the polymeric chain, high
stability,1 low cost,3 and ease of preparation.4 COPs have a
wide range of applications in the elds of sensors,5,6 actuators,7
rechargeable batteries,8 solar cells,9 electrochromic display
materials,1 anticorrosion protection,10 and electromagnetic
shielding technology.11 For conduction, COPs can be doped
either p-type (oxidation) or n-type (reduction), depending on
the nature of the polymer.12 Polyaniline (PANI), polyacetylene
(PA), polythiopene (PT), polyparaphenylene (PPP), polyparaphenylenevenylene (PPV), and poly(o-phenylenediamine)
(POPD) are prominent examples of COPs.13 The COP family
received another important member when, in the 1960s, Weiss
et al. prepared polypyrrole (PPy) by the pyrolysis of
tetraiodopyrrole.14 The authors concluded that PPy can
2014 American Chemical Society

Received: June 6, 2014

Revised: July 15, 2014
Published: July 18, 2014
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reliably predicts the excitation energies and oscillator strengths

for a wide range of molecules.3537 These molecules may be
from small to large ones, including higher fullerenes, organic
and inorganic molecules, biologically important systems, and
transition-metal complexes.35,36 TD-DFT calculations can
incorporates environmental eects and quickly give the best
quantitative t to UVvis spectra (excitation energy) of these
molecules, especially using hybrid functionals (B3LYP).3739
DFT is the only approach that can handle long -conjugated
radicals without spin contamination in the unrestricted openshell formalism. Hence, we used the UB3LYP level of theory
for our target species. In the case of approximate DFT, negative
orbital energies (HOMO and LUMO) do not give accurate
ionization potentials (IP) and electron anities (EA), but the
deviation is about 1 eV. Since the error is method-dependent
and consistent for all oligomers, orbital energies can be still
used to examine trends consistently.40 DFT at the UB3LYP/631G(d)4148 level of theory was employed, as discussed in our
previous work.5,6,11 Geometries of the neutral, cationic, and
dopantnPy oligomers were optimized at the above-mentioned
level of theory. NH3 acts as a Lewis base in the gas phase, while
neutral Cl is a radical that can neither accept nor donate an
electron pair. Whether neutral Cl donates or accepts an
electron pair is also investigated here. Neutral Cl and NH3 were
reacted with 9Py (Cl-9Py and NH3-9Py, respectively); NH3 was
also treated with 9Py+ (NH3-9Py+) for the investigation of its
dedoping process. The selected species were conrmed to be
true minima on the potential energy surface using frequency
calculation (no imaginary frequency). According to the
literature, the equilibrium structure of pyrrole oligomers is
nonplanar.33,49 Thus, this minimum was used for all species
(complexes). The nonplanar structure was found to be a
minimum in all cases (except for 9Py+, which is planar). The
geometric, vibrational, and electronic properties of the nPy
oligomers with up to nine repeating units were evaluated
theoretically, and the calculated properties were extrapolated to
those of polymeric PPy through a second-order polynomial t.
A uniform scaling factor of 0.961350 is used for the vibrational
wavenumber, obtained from the DFT calculations. The uniform
scaling factor is very appropriate for our system and can be
applied to a system with partial bonding, as reported by Halls et
al.51 Moreover, some interesting literature52,53 and our previous
experience11 also conrm that this scaling factor is suitable for
conjugated systems. However, dual scaling factors were also
used in the literature to improve the agreement between
simulated and observed frequencies. In a dual scaling
procedure, ngerprint and functional group regions should be
scaled with two dierent scaling factors.51,54,55 The changes in
band gap, conductivity, and resistance of nPy and nPy-X [where
X = +, NH3 and Cl (radical)16,40,47] are related to and
correlated with the perturbation in the vibrational spectra and
electronic properties. The latter include IP, EA, highest
occupied molecular orbital (HOMO), lowest unoccupied
molecular orbital (LUMO), band gap, UVvis (especially
max), natural bond orbitals (NBO),56 and Mulliken charge
analysis.57,58 All calculations were performed in the gas phase.

The conducting properties of COPs mainly depend on the

arrangement and number of their repeating unit and can be
reversibly tailored from insulator to semiconductor and then to
metal by doping, with insertion of p-type or n-type carriers.22
One of the major applications of COPs is in organic
photovoltaic cells, wherein free charge generation is because
of electron transfer from dopant (donor) to polymer
(acceptor). The device performance depends on the charge
injection, transfer, balance, and exciton connement.2 Furthermore, photoelectrochemical properties of a photocatalyst
can be enhanced by structural doping and substitutional and
interstitial doping.23 Selection of a proper doping agent for
COPs reduces the energy gap, enhances the visible light
absorption, facilitates charge carrier mobility, and favors the
separation of photogenerated electronhole pairs.23 The
presence of counterions (dopants) in COPs is theoretically
investigated, and these counterions can modify charge
distribution and aect the extent of charge delocalization.24,25
In 1984, Bredas et al.25 reported the rst theoretical study on
the doping of PPy using ab initio methods (HartreeFock/
STO3-21G); however, their study was restricted to optimized
geometric structures and orbital analyses. Alkan and Salzner
studied the doping process of thiophene oligomers, using
density functional theory (DFT).26 They reported that lightly
doped chains contain electron polarons in oligothiophene in
the presence of dopants (counterions), but these polarons are
delocalized over the entire backbone in the absence of the
counterions. Ecient nonoxidative doping and dedoping
phenomena are also observed in COPs, especially, in PANI.
In this process Lewis acids and bases are reacted with polymer,
which result in conductivity changes, control of conjugation
lengths, color changes, and switch of states of COPs.27,28
Studies on the oxidative and nonoxidative doping and
dedoping of polythiophene and PANI have been reported to
some extent both theoretically and experimentally; however, a
comparative investigation of the doping and dedoping process
of PPy has not yet been performed. In the present work, we
present a study of the doping and dedoping process of PPy
oligomers with up to nine repeating units using hybrid DFT
methods and its comparison with earlier theoretical and
experimental work. In the oligomeric studies of systems with
six to eight repeating units, convergence of the various physical
properties toward those of the polymers can be assumed, as has
been proven by several theoretical studies, including those from
our group.4,5,14,29

2. COMPUTATIONAL METHODS
All calculations were performed with Gaussian 09.30 The
visualization of results was achieved through Gabedit31 and
GaussView 5.0.9.32 DFT and time-dependent DFT (TD-DFT)
calculations were performed to investigate the doping process
of nPy oligomers (where n = 19) and PPy. It was previously
observed in a number of reports5,33 that 9Py can accurately
represent the characteristics of the polymer. HartreeFock
(HF) at the TD-HF level is very accurate to determine the
excitation energies of neutral -conjugated systems, but it fails
for the open shell systems because of spin contamination;14 for
details, see ref 34. HF underestimates excitation energies for
charged -conjugated systems, while TDDFT with a hybrid
functional does not and even does not suer from spin
contamination for nPy oligomers. From a computational cost
and accuracy point of view, TD-DFT is an intermediate theory
between semiempirical and wave function approaches that

3. RESULTS AND DISCUSSION

Optimized Geometric Structures. The largest oligomer
with nine repeating units (9Py) best represents the structural
properties of the polymer (PPy), and hence, we restrict the
discussion to 9Py and its derivatives.
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Figure 1. Optimized geometric structure of 9Py, 9Py+, 9Py-Cl, 9Py-NH3, and 9Py+-NH3.

9Py. Optimized geometric structures of 9Py, 9Py+, 9Py-NH3,

9Py+-NH3, and 9Py-Cl are given in Figure 1. The optimized
geometric parameters, such as bond lengths, angles, and
dihedral angles of the neutral and doped Py oligomers, are
compared in Table 1 to the earlier theoretical results of Bredas
et al.25 and with the X-ray data on small Py oligomers such as
bipyrrole and terpyrrole.25,59,60 Selected optimized geometric
parameters of these ve species are given in Table 1. (See
Figure 2 for a denition of the various geometry parameters.)
Figure 2. Structure of PPy.

Table 1. Optimized Geometric Parameters of 9Py, 9Py+,

9Py-Cl, 9Py-NH3, and 9Py+-NH3 with Reference to Figure 2
species

rCC ()

bCC ()

rCN ()

aCNC (deg)

9Py
9Py+
9Py-Cl
9Py-NH3
9Py+-NH3

1.40
1.40
1.40
1.40
1.40

1.44
1.42
1.41
1.44
1.42

1.37
1.37
1.36
1.37
1.37

110.82
110.65
109.80
109.93
109.75

The rCC, rCN (internal ring bond distances) and bridging

bond distances (bCC) at the UB3LYP/6-31G(d) level of
theory are found to be 1.40, 1.37, and 1.43 , respectively, for
9Py. The internal ring angle (aCNC) in all Py repeating
units is found to be about 110.82. All these parameters of the
neutral species are consistent with the earlier computational
and experimental data.25,59,60
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Figure 3. Bond length changes along the polymeric backbone of 9Py, 9Py+, 9Py-Cl, 9Py-NH3, and 9Py+-NH3 with reference to Figure 2.

9Py+. Upon removal of one electron from 9Py, the bridging

bond distances (bCC) and internal ring angle (aCNC)
decrease to 1.42 and 110.65, respectively. However, the rest
of the geometric parameters remain essentially the same,
although a planar geometry results due to the generation of the
conducting form.
9Py-Cl. Doping of 9Py with Cl, resulting in 9Py-Cl, has a
rather severe eect on its ground-state geometry. The angle
aCNC also decreases to 109.80, which is a consequence of
the decrease in resistance over the polymeric backbone.5
9Py-NH3. From an analysis of the results in Table 1 it can be
easily concluded that NH3 has very little eect on the polymeric
chain of 9Py; only the internal rings are found to be aected.
NH3 decreases the aCNC bond angle by about 0.31.
9Py+-NH3. The interaction of ammonia with 9Py+ is also
evaluated for its reducing power in dedoping process. The
optimized geometric parameter of 9Py+ and 9Py+-NH3 are
nearly the same, except for the internal angle, which increases
from 110.65 to 111.13. This increase in the internal angle
increases the resistance over the polymeric backbone.
Comparative bond lengths of CN and CC along the
backbone of 9Py, 9Py+, 9Py-Cl, 9Py+-NH3, and 9Py-NH3 are
given in Figure 3.
Infrared Spectral Characteristics. Computed infrared
spectra of 9Py, 9Py+, 9Py-Cl, 9Py-NH3 and 9Py+-NH3 are given
in Figure 4. (See Figures S1S3 of the Supporting Information
for details.) Comparisons of the important band peaks of 9Py,
9Py+, 9Py-Cl, 9Py-NH3, and 9Py+-NH3 along with their
approximate assignments are collected in Table 2, where they
are also compared to the available experimental data.6164 (See
Tables S1S6 of the Supporting Information for details.)
Generalized gradient approximation (GGA)37,46,65 is also an
appropriate method for simulating the vibration spectra of a
nite and innite number of atoms. Clavaguera-Sarrio et al.66
reported that GGA can successfully predict the structural and
vibrational properties of closed and open-shell systems for
oxides of actinide compounds. Furthermore, they correlated the
reliability of GGA with CASPT2, which is a highly computationally demanding method. Adjokatse et al.67 had also
systematically studied the dielectric and piezoelectric response
of odd-numbered nylons with the help of the DFT method
with GGA and found nice correlation of the theoretically
simulated vibrational spectrum with that of available experimental data. For conducting polymers, literature reveals that

Figure 4. Scaled IR spectra of 9Py, 9Py-NH3, 9Py+, 9Py+-NH3, and

9Py-Cl.

pure GGA and hybrid B3LYP are quite eective at simulating

the vibrational spectra; however, the latter is more abundantly
used in the literature.37,52,65 Moreover, the B3LYP method has
produced the experimental data quite well (see Table 2 of the
text). Because of the nice correlation between theory (using
uniform scaling factor) and experimental data, we chose
B3LYP.
9Py. The simulated scaled IR spectrum of 9Py has two
prominent band peaks in the functional group region at ca.
3521 (expt 3404 cm1, NH stretching) and 3118 cm1 (expt
2920 cm1, CH stretching).6164 Some characteristic band
peaks in the ngerprint region for conjugation in the polymeric
backbone of 9Py (as discussed by Omastova et al. and Zerbi et
al.61,64) are 1396 (expt 1400, NH wagging), 1297 (expt 1312,
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Table 2. Experimental IR and Calculated Frequencies (in cm1) of 9Py, 9Py+, 9Py-Cl, 9Py-NH3, and 9Py+-NH3a
calcd frequency
no.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
a

expl16,6873 IR
3403

9Py

9Py+

3521

3519

3521

3118

3145

3145

2920

9Py-Cl

9Py-NH3
3521
3440
3160
3117

9Py+-NH3

approx assignment

3519

NH
NH of NH3
NH
CH
NH (near NH3)
CH (near Cl)
NH (near Cl)
cis of NH3
CC; wag CH, HN
CC; wag CH, NH
NC; wag CH, NH
NC, CC; wag CH, NH
NC, CC; wag NH, CH
NC, CC; wag NH, CH
CC; CH; cis CNC
CC; wag NH
wag CH, NH; NC
cis CH, NH
wag CH, NH
Cis CH
rings breathing
def(ring)// CH, NH
CH, NH
CH, NH
CH, NH
NH

3144
3083

3072
2540
1653

15501460
1514
1484
1440
1400
1312
1250

1220
1081
1050
990
930

1396
1297
1218
1095
1051

856
734
680
426

1575
1537
1500
1463
1439

1542

1208
1099

1474
1453
1386
1304
1268
1202
1096

1027
994
874
743

1030
971
865
769/737

594
457

457

1313

1517

1579
1544

1440
1396
1287

1470
1440
1377
1312

1217
1094
1052
1036
874
731
679
462/447

1213
1100
1026
965
874
742
595
456

, stretching; wag, wagging; cis, scissoring; , bending; def, deformation mode; , out-of-plane bending.

Moreover, some new bands appear in the functional group and

ngerprint regions. The two new peaks in the functional group
region at ca. 3072 and 2540 cm1 are due to the presence of a
counter species, such as Cl in this case, and have assignments of
CH and NH stretching, respectively. Compared to neutral
9Py, ve new bands appear at ca. 1474 (CC stretching),
1453 (CH bending), 1268 (NH bending), 1030 (CH
scissoring), and 971 cm1 (ring breathing). The increased
number of band peaks in the 1600900 cm1 region means
that Cl has caused longer -electron conjugation in the
polymeric backbone of 9Py.
9Py+-NH3. To investigate the dedoping process of 9Py+
through IR spectral analysis, an ammonia molecule was placed
near the backbone with a suitable (optimized) distance.
Compared to the 9Py and 9Py+, the IR spectrum of 9Py+NH3 has an extra peak in the functional group region at 3083
cm1 (NH stretching ammonia). The band peak at ca. 1500
cm1 (CH, NH wagging and minor NC stretching) in the
9Py+ spectrum disappeared upon reaction with NH3. The
diminishing of this band in the 9Py+-NH3 complex is evidence
of the lower delocalized -electron conjugation, which means
that this analyte creates localization in the polymeric backbone.
Comparison of the various band frequencies of the 9Py+ and
9Py+-NH3 (Figure 4 and Table 2) led us to conclude that NH3
causes a blue-shift in the frequencies of 9Py+, a consequence of
the dedoping phenomena.
UVVisible and UVVisNear-IR Spectroscopic
Study. Polaron states are generally formed in -conjugated
systems such as oligomers of PPy.4,7478 These polarons may
be localized or delocalized depending on the amount and
nature of dopant. When the number of polarons increase, then

NC stretching), 1218 (expt 1220, CH wagging), and 1095

cm1 (expt 1081, CH wagging). Dierences between
experimental and simulated frequencies are primarily due to
the comparison of condensed phase (experimental) and gasphase simulation. This has been discussed in the literature in
fairly good detail.16,6873
9Py-NH3. Compared to 9Py, 9Py-NH3 has three additional
band peaks in the functional group region (Figure 4), 3440
(NH stretching, ammonia), 3160 (NH stretching, 9Py), and
1653 cm1 (HNH scissoring, ammonia). Two band peaks at
ca. 1440 and 1036 cm1 in the IR spectrum of 9Py-NH3
provide evidence of the presence of increased -electron
density in the polymeric backbone, compared to isolated 9Py.
As seen in Table 2, the other peaks in the ngerprint region are
not comparable for 9Py and 9Py-NH3.
9Py+. Removal of an electron from the backbone of 9Py
results in doping to form 9Py+, which causes red shifts in the IR
frequencies compared to those of the neutral 9Py. The higher
frequency bands in the functional group region, such as 3519
and 3145 cm1, have low intensity in 9Py+ but similar
assignments as those of the 9Py band peaks. Red shifts in the
frequencies of the ngerprint region are also observed and
some new band peaks appear at ca. 1537, 1500, 1439, 1027, and
994 cm1. Examining the IR spectrum of 9Py+ (Figure 4) and
its prominent band peaks as listed in Table 2 leads us to
conclude that the conductivity is increased, based on the
presence of strong band peaks in the 1600900 cm1 region
(vide infra). This statement also corroborates well with the
earlier reported work.16,6873
9Py-Cl. On comparison of 9Py-Cl with the neutral 9Py, we
notice that Cl causes red-shifting in the IR spectrum of 9Py.
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For 9py+, * (415 nm) and midgap transitions (560

nm) are considerably red-shifted compared to the neutral 9Py
(vide supra). The 414 nm peak of 9Py is replaced by a
delocalized polaron band (transition from the valence band to
the lower polaron band) at 1907 nm in 9Py+. On reacting NH3
with 9Py+ (Figure 6), a blue-shift (1907 1829 nm) is
observed in its max. This blue-shifting can also be assigned to
the dedopoing process of 9Py+, which consequently results in
decreased conductivity, delocalized -conjugation length, and
an increase in the band gap.4,1518,7476
Interaction of Cl with 9Py causes formation of a localized
polarion (polaron formation in the presence of a counter
species) characterized by an absorption band at 1242 nm
(transition from the valence band to the lower polaron band).69
The * and midgap transitions are signicantly redshifted to 466 and 528 nm, respectively (Figure 7). The
absorbance band at 528 nm for 9Py-Cl (and also 560 nm for
9Py+) is indicative of extended -conjugtion length.
The peaks in the near-IR region at 1907 nm (in Py+) and
1242 nm (in 9Py-Cl) are due to delocalized and localized
polaron structures, respectively. A polaron is localized in the
presence of a counterion (9Py-Cl), whereas it is delocalized in
the absence of any counterion (9Py+). In summary, the
ionization process converts polarons into localized (in the
presence of a counter radical) and delocalized (absence of a
counterion such as in the case of 9Py+) polarons (extended conjugation length). The extension of the excitation energies
beyond 1800 nm under the polaron and bipolaron regime is the
result of the new transition energy levels between the
conduction and valence bands. The presence of localized and
delocalized polarons allows one to draw conclusions regarding
the doping level and conductivity, optical, and electronic
properties of CPs, especially in the case of PPy and
PANI.4,1518,7476
Natural Bonding Orbital and Mulliken Charge
Analysis. Charge transfer phenomena between the nPy and
dopants (NH3, Cl) are simulated by Mulliken (QMULLIKEN) and
NBO (QNBO) charge analysis at the UB3LYP/6-31G(d) level of
theory. These properties are basis set dependent; however, if
the same level of theory is used for dierent structures [such as
UB3LYP/6-31G(d) or UB3LYP/6-311++G(d,p)], then the
results will provide trends and therefore be meaningful. The
basis set dependence of these charge analysis tools has been
discussed by Fonseca Guerra et al.57 and Martin et al.58
The net charge transfer in 9Py-NH3 from ammonia to 9Py is
0.047 e and 0.046 e, based on QNBO and QMULLIKEN,
respectively. The NH3 transfers about 0.057 e based on QNBO
and 0.065 e based on QMULLIKEN to 9Py+. In the case of the Cl
dopant, Cl receives about 0.801 e charge based on QNBO and
0.705 e based on QMULLIKEN from 9Py. From this charge
analysis it can be easily concluded that, in the 9Py-Cl complex,
Cl has caused oxidation in the 9Py (doping). However, in the
case of the 9Py+-NH3 complex, reduction in the 9Py+ is
observed (dedoping).
HOMO and LUMO Energy. The HOMO and LUMO of
9Py, 9Py+, 9Py-Cl, 9Py-NH3, and 9Py+-NH3 calculated at
UB3LYP/6-31G(d) are shown in Figure 8, and their
corresponding energies from monomer up to innity are listed
in Tables 35. (See the Supporting Information, Figures S8
S13, for pictures of individual HOMOs and LUMOs.)
Frontier Orbitals of 9Py vs 9Py+. Figure 8 provides
comparisons of the HOMO and LUMO of the neutral 9Py
and cationic species (9Py+). The HOMO of 9Py+ extends over

they are converted (through an ionization process) to

bipolarons, which means the presence of two similar charges
on the same molecule, usually at the terminal of a polymer/
oligomer backbone. UVvis spectroscopy is a useful tool to
dierentiate between polarons and bipolarons and has widely
been examined theoretically and experimentally by the
MacDiarmid and Bredas groups.4,7478
The UVvis and UVvisnear-IR spectra of 9Py and 9Py-X
(where X = +, Cl, and NH3) have been simulated in the gas
phase at the TD-DFT/UB3LYP/6-31+G(d,p) level of theory
(Figures 57). Our simulated UVvis spectrum of the neutral

Figure 5. UVvis spectra of 9Py (red) and 9Py-NH3 (black).

Figure 6. UVvis of 9Py+ (red) and 9Py+-NH3 (black).

Figure 7. UVvis of 9Py (red) and 9Py-Cl (black).

9Py is in close agreement with the reported experimental and

theoretical data.14,79 Three prominent peaks are observed in the
UVvis spectra of PPy: 274 nm ( *), 331 nm (midgap
transition), and at 414 nm (max, transition from the valence
band to the conduction band). Doping of 9Py oligomers with
NH3 molecules (shown in Figure 5) causes slight red-shifting in
its max (414 416 nm), while a slight blue-shift is observed in
the midgap transition (331 329 nm). The red-shifting in max
with NH3 dopant illustrates its n-type doping nature (basic
nature, dedoping). With a decreasing band gap, conduction and
delocalization are slightly enhanced in 9Py-NH3 compared to
9Py (vide infra). The blue-shifting in the second peak (331
329 nm) of 9Py-NH3 is due to distortion (quinoid form) in the
regular pyrrole rings (vide supra), resulting in a decrease of
interband transition.
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Figure 8. HOMO and LUMO of the 9Py, 9Py+, 9Py-Cl, 9Py+-NH3, and 9Py-NH3 complexes.

Table 3. IP, EA, HOMO Energy, LUMO Energy and Band

Gap in eV of nPy

Table 5. IP, EA, HOMO, LUMO and Band Gap in eV of

9Py, 9Py-NH3, 9Py-Cl, and 9Py+-NH3

na

IP

EA

HOMO

LUMO

band gap

species

IP

EA

HOMO

LUMO

band gap

1
2
3
4
5
6
7
8
9
10

5.48
4.75
4.43
4.26
4.17
4.11
4.06
4.03
4.01
3.99
3.80

1.38
0.35
0.03
0.25
0.38
0.46
0.53
0.57
0.6
0.63
0.90

5.48
4.75
4.43
4.26
4.17
4.11
4.06
4.03
4.01
3.99
3.80

1.38
0.35
0.03
0.25
0.38
0.46
0.53
0.57
0.60
0.63
0.90

6.86
5.10
4.40
4.01
3.79
3.65
3.53
3.46
3.41
3.36
2.90

9Py
9Py-NH3
9py-Cl
9Py+
9Py+-NH3

4.01
3.85
4.28
6.26
6.16

0.60
0.46
1.21
3.35
3.20

4.01
3.85
4.28
6.26
6.16

0.60
0.46
1.21
3.35
3.20

3.41
3.39
3.07
2.91
2.96

energies of 9Py are 4.01 and 0.60 eV, while for 9Py+ they
are 6.26 and 3.35 eV, respectively. The higher magnitude of
the HOMO energy (6.26 eV) of the 9Py+ is a consequence of
the existence of a longer conjugation length (vide infra),
delocalization of -electron density, and high conductivity, in
addition to being a charge eect.
Frontier Molecular Orbitals of 9Py vs 9Py-NH3. From
Figure 8, frontier molecular orbitals of 9Py and 9Py-NH3
species can be comparatively analyzed. NH3 is a reducing
agent, as has already been discussed in the analysis of 9Py and
9Py-NH3 molecular orbitals. Ammonia has reduced in
magnitude both the HOMO and LUMO energies of the 9Py,
from 4.01 to 3.85 eV and 0.60 to 0.46 eV (Table 5). It
also decreased the -electron density over the 9Py polymeric
backbone, resulting in an increase in resistance.
Frontier Molecular Orbitals of 9Py+ vs 9Py+-NH3. Contours
of the HOMO and LUMO of 9Py+ and 9Py+-NH3 are given in
Figure 8. NH3 has caused a slight decrease in magnitude of the
HOMO and LUMO energies of 9Py+-NH3 (compared to
9Py+). Figures 1 and 8 show clearly that NH3 has led to slight
bending of the terminal rings of the polymer, compared to the
other cases. Moreover, Figure 8 shows that NH3 decreases the
delocalization of the -electron density, resulting in lower
conductivity. (See the discussion of the band gap, vide infra,
and dedoping phenomena.) These results also support the
earlier conclusions from the analysis of the UVvisnear-IR
spectra, optimized geometric parameters, and IR spectral
characteristics. The estimated HOMO and LUMO energies

n is the number of repeating units.

Table 4. IP, EA, HOMO Energy, LUMO Energy and Band

Gap in eV of nPy+, where

na

IP

EA

HOMO

LUMO

band gap

1
3
5
7
9
11

13.09
8.6
7.32
6.68
6.26
5.97
4.91

6.21
4.75
4.09
3.67
3.35
3.07
2.41

13.09
8.60
7.32
6.68
6.26
5.97
4.91

6.21
4.75
4.09
3.67
3.35
3.07
2.41

6.28
3.85
3.23
3.01
2.91
2.90
2.46

n is the number of repeating units.

all carbons, hydrogens and nitrogens and forms a planar

structure that involves delocalization of the -electrons over the
entire molecular backbone, contrary to its neutral counterpart
9Py. On the other hand, only the central atoms contribute to
the LUMO; therefore, the LUMO is localized in the polymeric
framework. The HOMO and LUMO energies of nPy and nPy+,
from monomer up to innite repeating units, are given in
Tables 3 and 4 (vide infra). The estimated HOMO and LUMO
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Figure 9. Energy level diagram of 9Py (a) and 9Py-NH3 (b).

of 9Py+-NH3 are 6.16 and 3.20 eV, respectively (Table 5).

The HOMO and LUMO energies of the 9Py+-NH3 complex
are 0.10 and 0.15 eV lower in magnitude than those of 9Py+.
Frontier Molecular Orbitals of 9Py vs 9Py-Cl. Molecular
orbitals (HOMO and LUMO) of 9Py and 9Py-Cl are given in
Figure 8, and the corresponding estimated energies are listed in
Table 5. Analysis of the optimized geometric structure (vide
supra) and molecular orbitals led us to conclude that Cl
planarizes the geometry of 9Py and extends the -electron
conjugation density over its polymeric backbone. This extended
-electron conjugation density increases the conductivity and
decreases the band gap (vide infra) and resistance in the
polymer. This statement conrms and extends the mentioned
characterizations of the Cl doping for 9Py (or PPy). The
presence of Cl radical aects the HOMO and LUMO energies
of 9Py by about 0.27 and 0.61 eV, respectively.
Electronic Properties like IP, EA, and Band Gap. It is
also very well-known from the literature5,6,34,42,80 that the IP
and EA obtained from the negative values of the DFT orbital
(HOMO and LUMO) energies (Koopmans theorem) with
typical approximate exchange correlation functionals is usually
too small as compared with experimental values. However,
hybrid functionals (such as UB3LYP), which account for the
eects of self-interaction to some degree, result in a better
correlation (vide supra).
The IP, EA, and band gap of nPy, nPy+, 9Py-Cl, 9Py+-NH3,
and 9Py-NH3 are listed in Tables 35. The band gap values
along with their valence, conduction, and polaron bands are
given in Figures 911. Comparisons of the IP, EA, and band
gap of these ve dierent species, restricted to nine repeating
units, are listed in Table 5. Increasing conjugation (as explained
in the frontier molecular orbital analysis) over the polymeric
backbone causes higher IP and EA and decreased band gap.
The band gap is estimated from the dierence of the valence

and conduction bands orbital energies (HOMOLUMO).

The IP and EA of 9Py are 4.01 and 0.60 eV, respectively, and its
band gap (3.41 eV), along with valence and conduction band
energies, is given in Figure 9a. The valence and conduction
bands of 9Py are at 4.01 and 0.60 eV, respectively, while the
interband or midgap transition is at about 2.99 eV above the
valence band. Ammonia (donor) decreases the IP and EA
values of 9Py by about 0.16 and 0.14 eV, respectively, as it has
donated electrons to the 9Py orbitals (Table 5 and Figure 9b).
Furthermore, we see from Figure 9b that the valence and
conduction bands of 9Py-NH3 are at 3.85 and 0.46 eV,
respectively. Its band gap is 3.39 eV, while the midgap
transition is at 2.97 eV.
As another attempt to conrm the dedoping process of PPy
with NH3, NH3 is reacted with 9Py+ and characterized with IP,
EA, and band gap analysis, as shown in Figure 11a and Table 5.
Analysis of Figure 11a leads us to conclude that NH3 causes
dedoping of PPy and decreases the IP and EA of Py+. The
valence, conduction, and localized polaronic bands of Py+-NH3
are at 6.16, 3.20 and 0.67 eV, respectively. NH3 has
increased the band gap of Py+ (Py+-NH3) from 2.91 to 2.96 eV.
The decrease in IP and EA of 9Py+ by NH3 is about 0.10 and
0.15 eV, respectively. The lower IP, lower EA, and increased
band gap show that the polymer is reduced (dedoped).
Moreover, it also demonstrates reduced delocalization of electron (vide supra).
Cl has caused oxidation (doping) in 9Py, as can be seen from
the data of Table 5 and Figure 11b. Cl attracts electrons from
the orbitals of 9Py, consequently increasing its IP and EA values
by about 0.27 and 0.60 eV, respectively. Simultaneously, with
the increasing of these values, its band gap decreases from 3.41
to 3.07 eV.
Table 5 and Figure 12 show that, when 9Py is oxidized in the
absence of a counterion, its IP and EA increase by about 2.25
and 2.75 eV, respectively. Its band gap (2.91 eV) also decreases
by about 0.51 eV compared to that of neutral 9Py. The
decrease in band gap of nPy+ from the monomer (n = 1) up to
the innite polymer (n = ) is given in Figure 13. The valence
and conduction bands are situated at 6.26 and 3.35 eV,
respectively. Another prominent band, which can be identied
as a delocalized polaron, is located at 0.65 eV. This delocalized
polaron band is responsible for the high conductivity and lower
resistance and band gap value of 9Py+. An interband transition
from the singly bonded polaron state to the antibonding
polaron state (nonbonding polaron) has an energy of 2.21 eV.
This delocalized polaron transition (bonding to antibonding) is
responsible for the delocalized extended -electron conjugation
over the polymeric backbone of 9Py+.

Figure 10. Developments of band structure of PPy from energy levels

of oligomers. (The monomer is used as a repeat unit.)
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Figure 11. Energy level diagram of 9Py+-NH3 (a) and 9Py-Cl (b).

as in 9Py+ and causes red-shifts in the IR frequencies. The

doping process of 9Py is also achieved on reacting with Cl. This
results in the emergence of ve new bands in the 1600900
cm1 region. Dedoping of 9Py+ is achieved when ammonia is
added; consequently, some bands in the 1600900 cm1 region
disappear, and the result is lower delocalized -electron
conjugation. In the UVvis and UVvisnear-IR spectra, the
addition of dierent analytes (dopant) to 9Py results in the
disappearance of certain bands and gives rise to some new
absorbances corresponding to localized and delocalized polaron
bands. Specically, the peaks in the near-IR region at 1907 nm
for Py+ and 1242 nm for 9Py-Cl are due to delocalized and
localized polaron structures, respectively. The presence of
localized and delocalized polarons in the UVvis near-IR
spectra is correlated with the doping level, conductivity, optical,
and electronic properties of CPs, especially in the case of PPy
and PANI.4,7476 It can also be concluded that the polarons/
bipolarons fall in the visible and near-IR region. Thus, they
actually aect the vibrational, electrical, optical, and electronic
properties of CPs. The net charge transfer in theses complexes
is simulated with NBO and Mulliken charge analysis. NH3
transfers charge to 9Py and 9Py+, while Cl receives charge from
9Py, conrming the dedoping and doping phenomena,
respectively. Frontier molecular orbitals (HOMO and
LUMO), IP, EA, and band gap are also consistent with the
vibrational and UVvisnear-IR spectroscopy. The electron
density in the MOs extends over the polymeric geometry in the
case of 9Py+ and 9Py-Cl, while this is reversed in 9Py+-NH3
compared to neutral 9Py. In the case of oxidation and Cl
dopant, the IP and EA increase, and consequently, there is a
decrease in the band gap.

Figure 12. Energy level diagram of 9Py+.

Figure 13. Developments of band structure of PPy+ from energy level

of oligomers. (The monomer is used as a repeat unit.)

4. CONCLUSION
DFT calculations have been carried out on a number of
molecules with dierent characteristics, notably, 9Py, 9Py+,
9Py-Cl, 9Py+-NH3, and 9Py-NH3, to investigate their doping
and dedoping processes. In the vibrational analysis, the band
peaks in the 1600900 cm1 region give information about the
short and extended -electron conjugation length. The number
of peaks in this region is evidence of the presence of
conjugation in the polymeric backbone. This is further
conrmed from the high IP, high EA, low band gap, as well
as the high electron density of the HOMO and LUMO. Slight
dierences are found between experimental and simulated
frequencies; however, these are due to the condensed and gasphase IR spectra, respectively. Compared to neutral 9Py, the
dierent additives (NH3, +, Cl, etc.) result in extra band peaks
both in the ngerprint and functional group regions. Removal
of an electron from the backbone of 9Py results in doping such

ASSOCIATED CONTENT

S Supporting Information
*

IR and UVvis spectra, diagrams of HOMO and LOMO

orbitals, and tables of selected IR band peaks along with
approximate assignments. This material is available free of
charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION

Corresponding Authors

*A.-u.-H.A.S. tel, +92-91-9216652; e-mail, anwarulhaqalishah@

upesh.edu.pk.
*K.A. tel, +92-992-383591; e-mail, kayub@kfu.edu.sa,
khurshidayub@gmail.com.
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The Journal of Physical Chemistry C

Article

Author Contributions

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The manuscript was written through contributions of all

authors. All authors have given approval to the nal version of
the manuscript.
Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
We gratefully thank Prof. Ulrike Salzner and Prof. Georg
Schreckenbach for his valuable comments, suggestions and
discussion. We acknowledge the Institute of Chemical Sciences
(ICS), University of Peshawar and Higher Education
Commission, Islamabad.

ABBREVIATIONS
DFT, density functional theory; PPy, polypyrrole; B3LYP,
Becke 3 parameter exchange functional combined with the
LeeYoungParr correlation functional; HOMO, highest
occupied molecular orbital; LUMO, lowest unoccupied
molecular orbital; IP, ionization potential; EA, electron anity;
NBO, natural bonding orbital.

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