Journal of Science and Technology

ISSN: 2456-5660 Volume 3, Issue 06 (NOV -2018)

www.jst.org.in DOI:https://doi.org/10.46243/jst.2018.v3.i06.pp68- 89

Effect of Inorganic Acids and Salt on the Conduction

Behaviour of PANI Composites by DFT and Experimental
Studies
A. Ananda Jebakumar
Department of Chemistry, Government Polytechnic College for Women, Madurai,
Tamilnadu, India-625011

To Cite this Article

A. Ananda Jebakumar|, “Effect of Inorganic Acids and Salt on the Conduction Behaviour of PANI
Composites by DFT and Experimental Studies ” Journal of Science and Technology, Vol. 03, Issue
06,- November-December 2018, pp68-89

Article Info

Received: 27-10-2018 Revised: 07-11-2018 Accepted: 17-11-2018 Published: 27-11-2018

Abstract
Electroactive composite materials are a new generation of smart materials based
on intrinsically conducting polymers like PANI. Here the computational and
experimental study of polyaniline (PANI) composites of inorganic acids and salt are
reported. The conductance is governed by charge mobility in the field produced
between counter ions. Size, oxidation state and electron deficiency governs the
conductance.
Keywords: PANI, Conductance, DFT, Spectral.
1. Introduction
Role of science is to alter nature for wellbeing [1]. Nowadays a great demand is
created for energy harvesting, transport and storage [2]. In this path conductance plays
a major role and modern synthetic metal, the conducting polymers are a great
alternative for metal for its economic value, easy to process and maintenance [3].
Chemistry is fascinating because a small change in the chemicals gave a lot of variation
in their property [4]. Such a slight as well as useful modification in the structure can be
easily done through compositing [5]. In this background polyaniline (PANI) is a
potential conducting polymer of academic and industrial value for designing [6]. PANI
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has many forms and protonated form of neutral emeraldine base derived from aniline is
mentioned as PANI [7] and it has lot of appreciations [8]. Role of research is to modify
a material into a new one of the desired value [9]. In this sense understanding, the
characters of the compound are essential. For the understanding of compounds,
quantum mechanical calculation along with experimental study plays a major role [10].
DFT is a type of computational method by which the character such as structure and
electronic effects can be accomplished in a good manner [11]. Among the experimental
studies, spectra and electrical conductance are useful. In this scenario the properties as
well the behaviour of PANI can be studied by composting. A vast majority of classes of
compounds are available for the study of composites but inorganic and their salts may
be helpful. Thus four different concentrations of PANI composites with inorganic acids
and salts (IAS) are synthesised and studied by DFT, spectra and conductance. The
inorganic acids studied are boric acid (BA), potassium dihydrogen ortho phosphate
(PDHOP), molybdic acid (MA), phosphotungstic acid (PTA) and inorganic salt is
sodium hypophosphate (SHP).
2. Experimental
2.1 Synthesis of PANI
All the chemicals used were of AR grade obtained from Merk, India and used as
such.
10 g of aniline and 30.6 g of ammoniumperdisulphate were dissolved in 1M 250ml HCl
separately and cooled them at 18°C. Ammoniumperdisulphate solution was added
dropwise to the aniline solution with constant stirring for about 50 minutes.The content
was kept aside for 12 hours and washed with water containing small amount of acetone.
Then the content was filtered, dried at 80oC for 8 hours and stored in a polyethylene
container. Water was used as solvent. The yield is 58%. Basic unit weight is 92. The
percentage doping of HCl in PANI was measured by titrating a known amount of PANI
with standard alkali [12].
2.2 Synthesis of Composites
Slurry was prepared by 400 mg of PANI and 100 mg of BA in 4 ml of DMSO
for using mortar and pestle. The content was dried at 70 oC for 24 hrs. Weight loss
method was employed to check the complete removal of DMSO from the mixture. The
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ISSN: 2456-5660 Volume 3, Issue 06 (NOV -2018)
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composite was powdered and stored in a polyethylene container. The same procedure
was repeated with 200, 300 and 400 mg of SA and others.
2.3 Computation
DFT studies were performed by B3LYP/ 6-31G** basis set in gas phase at 25
°C using firefly software [13] in i7 computer. TDDFT calculations were done using
ORCA programme [14] by B3LYP/PBE0. Due to higher computational cost, the
modeling studies were carried for each one unit of phenyl and phenylene rings for PANI
and its composites.
2.4 Equipment
DC conductance was studied in Four Probe SES-Model DFP-RM. IR spectra
were recorded in JASCO FT/IR-4600, UV-VIS in JASCO V-650 (DMSO Solvent) and
Luminescence in Perkin Elmer, LS 45, excitation at 380 nm (DMSO Solvent). The
spectral studies used 80% PANI.
2.5 Analysis
Regression analysis was carried out for conductance studies. The equations used
were; for ideal-y = y0+ax; for real- y = y0+ax+bx2. The ideal behaviour means expected.
Pearson’s correlation coefficients for ideal and real behaviours were calculated using
software SPSS 16 [15].
3. Results and discussion
3.1 Stability and Structure
Due to higher computational cost the computations were studied for PANI-BA,
PANI-PDHOP and PANI-SHP. The details about the stability and structure are given in
Fig.1. Based on the stability values the phosphorus derivatives are more stable than
boron. Among the phosphorous derivatives, PANI-PDHOP is more stable than PANI-
SHP. The acid-salts are more stable than acids. The higher stability of PANI-PDHOP
may be due to the bigger size of potassium over sodium atom and higher oxidation state
of phosphorus in the later [16].
The structural parameters are given in Table 1. The order of binding of H1' with
N1 is PANI-PDHOP > PANI > PANI-BA > PANI-SHP with a magnitude of 28.8 %
higher and 3.2 and 6.4% lower than that of PANI. There is no much difference in the
bond length of other bonds and bond angles. The approaching angle of H1'-Cl2' to the
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Journal of Science and Technology
ISSN: 2456-5660 Volume 3, Issue 06 (NOV -2018)
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polymer concerned is 24.4 and 16.3% acute and 18.6% obtuse than PANI. Based on the
Cl2'-H1'-N1angle the position of H1' changed from PANI by 1.3, 24.8 and 4.2%
respectively for PANI-BA, PANI-PDHOP and PANI-SHP. Among them, both PANI-
BA and PANI-SHP have a lower value than PANI. Based on the stability and structure
the order of conductance is PANI-PDHOP > PANI-SHP > PANI-BA. The experimental
conductance is almost reverse of the above order. So the thermodynamic stability has an
adverse effect on the conductance due to larger separation between the energy bands
[17].
3.2 Charge Density
Table 2 has the charge density values. The charge density of H1' in PANI-
PDHOP is increased from PANI by 38.5%, while for others the values are decreased.
The same trend is repeated in the Cl 2'. This implies that H1' strongly bind with the PANI
skeleton in PANI-PDHOP. There is a small change in the charge density of other atoms.
Further a significant change in the charge density of N14, as it has a higher value than
PANI. These results infer that there is a charge localisation at N 14. The charge density
based order of conductance is PANI-PDHOP > PANI-BA > PANI-SHP. The order is
changed from the experimental conductance and this may be due to electron localisation
effect. Charge density reveals that phosphate is a better counter ion over borate. The
difference from the experimental conductance can be accounted by the bulkiness of
phosphate group and electron deficient nature of boron, which may cause higher
conductance in the latter [18].
3.3 Dipole moment
The values of the dipole moment are given in Table 3. All the composites have a
higher total dipole moment than PANI. This may be due to their acidic and salty nature.
The rate of increase in the total dipole moment from PANI is 72.7, 29.8 and 21.1%
respectively for PANI-SHP, PANI-PDHOP and PANI-BA. Along all the axis PANI-
SHP has the highest value of dipole moment. For PANI-PDHOP the higher dipole
moment value is in the x-axis. In PANI-BA the largest value of dipole moment is along
the y-axis. Molecular polarizability does not match with the experimental conductance
due to the higher electron localisation effect.
3.4 Molecular Orbital
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Journal of Science and Technology
ISSN: 2456-5660 Volume 3, Issue 06 (NOV -2018)
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Fig. 2 has the MO diagram of this system. The PANI-IAS formation can be
observable from the MO diagrams as the MOs of the PANI-IAS are different from the
PANI and their IAS. This implies that the compositing altered the energy levels in the
PANI-IAS [19]. The MOs of the PANI-IAS are comparable with PANI than additives.
There is a reasonable difference in the MOs of PANI-BA from others. For all the
composites the LUMO is the π* orbital of PANI. HOMO is concerned (Fig.3), for
PANI-BA it is on N1, PANI-PDHOP is Cl2' and PANI-SHP is O4". Unstable LUMO
caused by the change in the orientation of a molecule may lead to higher conductance in
PANI-BA [20].
3.5 TDDFT
Table 4 has the values of TDDFT. Both PANI-BA and PANI-SHP have one
transition each in the visible region. PANI-BA has three transitions in the UV region.
PANI-PDHOP has one transition in the UV region, while PANI-SHP has two
transitions in the UV region. Based on the computed optical band gap the order of
conductance is PANI-SHP > PANI-BA > PANI-PHOP. This order matches with the
experimental. The two VIS region transitions of the PANI-IASs are within the PANI
group. There is no charge transfer transition in the PANI-SHP. For others, the transition
in the UV region is of charge transfer transition from IASs to PANI. The transitions of
PANI-BA at 429.4, 310.5, 293.1 and 256 nm respectively for n→π* of the polymer
chain, n→π* of Cl2' to PANI, n→π* of Cl2' and O6", O4" to PANI and n→π* of O6",
O4" to PANI. For PANI-PDHOP, the only transition is n→π* of O2", O4" to EB. The
transitions of PANI-SHP at 443.7 nm, 322 nm and 299.4 nm are assigned for n→π* of
PANI, π→π* of ES and combination of n →π* and π→π* of PANI.
3.6 Frontier Molecular Orbital
Values of the above parameters are given in Table 5. Based on the bandgap the
order of conductance is PANI-PDHOP > PANI-SHP > PANI-BA > PANI. The
chemical stability and QMax also follow the same order. This implies that the PANI-IAS
has higher electron transfer ability over PANI and the above may be the order for the
conductance. The higher value of PANI-PDHOP may be due to its higher oxidation
state of phosphate. The values of PANI and PANI-BA are comparable. The additives
have the order PDHOP > SHP > BA. BA can transfer one electron while other two
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Journal of Science and Technology
ISSN: 2456-5660 Volume 3, Issue 06 (NOV -2018)
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electron. ΔQMax = -( + ) The ΔQMax values of PANI-BA and

PANI-SHP have negative value, but PANI-PDHOP has two units higher. This implies
that the PDHOP makes an impact on the PANI structure and enhance the PANI-
PDHOP's electron sharing effect. All the derived parameters favoured the higher
conductance for PANI-PDHOP.
3.7 Polarizability
The polarizability values are given in Table 6. PANI-PDHOP has very high γ
and α-also higher along the z-axis. The order of polarizability is γ > α > β. The
polarizability order of conductance is similar to charge density. This implies that
polarizability is not related to conductance.
3.8 Spectra
PANI-PTA has only spectral studies due to higher computational cost and
difficulty in making pellets for electrical studies. The IR spectra show the presence of
hydrogen bonding and C=N and C=C. Similarly, the electronic spectra indicate the
presence of n→π*, π→π* transition and polaron bands. The spectra are compared with
computation with correction for gas phase. The fluorescence spectrum of PANI-IAS has
two emissions in the visible region. The low energy emission is comparable for all the
PANI-IAS. There is a significant difference in the higher energy emission except for
PANI-MA and PANI-PTA.
3.9 Conductance
Conductance depends on thermodynamic stability, geometry, atomic charge
density/atomic polarizability/electron localisation and molecular polarizability/dipole
moment. The data related to the title are given in Table 7. The rate of change of
conductance of the composites is a function of a, b and x. For PANI-BA the
conductance decreased on the first addition of the BA and increased gradually for
further additions. This may be due to the small size of the BA and the presence of
electron deficient boron, which may reduce the electron density in the PANI and
consequently increase the conductance. From the observation of the PANI-BA graph,
the maximum deviation from the ideal behaviour is at 0.62 mole fraction of PANI.
Both the slope of the ideal behaviour and the restoring effect calculated from the

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Journal of Science and Technology
ISSN: 2456-5660 Volume 3, Issue 06 (NOV -2018)
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parameter 'b' of the PANI-IAS have comparable values. The restoring force to maintain
the ideal behaviour is 57% higher than that of 'a'.
For PANI-IAS such as PANI-PDHOP, PANI-SHP and PANI-MA the
conductance decrease for each addition of IASs. The higher amount of decrease is
observed in the case of PANI-SHP. It was expected that the conductance of the PANI-
IAS is to be increased from the PANI, but in reality the conductance of the PANI-IAS
are less than that of PANI. This may be due to the difference in the chemical behaviour
of PANI and PANI in PANI-IAS. The difference in the chemical behaviour of PANI
can be classified into two parts as, steric and electronic effects. The steric effect alters
the geometry of the molecule and retards the flow of electron. Further, the electronic
effect alters the conductance by localising the electrons. PANI-SHP conducts ten times
lesser than other PANI-IAS. Both PANI-MA and PANI-PDHOP have
comparable conductance. The order of conductance is PANI > PANI-BA > PANI-MA
> PANI-PDHOP > PANI-SHP. The order of 'a', 'b' and 'x' are PANI-SHP > PANI-MA >
PANI-PDHOP > PANI-BA and this is the order of deviation from the ideal or expected
behaviour. At higher concentrations of PTA, PANI-PTA could not be made into a
pellet.
4. Conclusion
In this work, computational and solid state behaviour of composites of PANI-
inorganic salt and acids are reported. The conductance of the polymer followed hoping
mechanism through the mobility of proton in the field produced between the polymer
chain and counterion. The criteria for higher stability in the PANI-IAS are a bigger size,
higher oxidation state, polarizability and salt form. Borate is a better counter ion than
phosphate due to its small size and electron deficient nature. Unstable LUMO and
higher oxidation state are related to the conductance.

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Figure 1 : Structure and Thermodynamic Stability

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Cl 2 '

6 7 H1 ' O H
9 10 5 ''
4 ''
H O
N 1 '' 2 '' B
5 1 N 3 ''
2
8 11 O
14
4 3 13 12 6 '' H 7 ''
H 15

ES-BA
(ES-BA- (ES+BA) = -36.4156 kJ/mole)

Cl2 '

H8 ''
H1 '
6 7 9 10
K O O
7 ''
N 11 1 '' 2 ''
5
2 1 N 14 P
8 3 '' O H
4 3 13 12 O 4 '' 5 '' 6 ''
H 15

ES-PDHOP
(ES-PDHOP- (ES+PDHOP) = -93.599 kJ/mole)

Cl2 '

H H 1 '' 2 ''
16
6 7 1' 9 10 O
Na H 6 ''
5
N 11 P
2 1 N 14
8 O 3 ''
4 '' H 5 ''
4 3 13 12 H 15

ES-SHP
(ES-SHP- (ES+ SHP) = -84.1472 kJ/mole)

C-Black; H-White; O- Red; N-Blue;Cl-Green;K,P,Na

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 Figure 2: MO Diagram

ES-SHP
ES-PHOP
BA PDHOP SHP ES ES-BA

78
 Figure 3: MO Number, Name, Energy(eV) and AO Contribution to MO

PDHOP
BA SHP
16 -HOMO (-8.362) 17 -LUMO (1.249) 34 -HOMO (-5.905) 35 -LUMO (-1.592) 22 -HOMO (-6.710) 23 -LUMO (-1.439)
O2''-1pz; O2''-2pz H7''-2s; H5''-2s O4''-1pz; O4''-2pz K1''-5s; K1''-4s O4''-1py; O2''-1px Na1''-4s; Na1''-2px

ES-BA

65-HOMO-8 (-8.272) 67-HOMO-6(-8.150) 73 -HOMO (-6.525) 74 -LUMO (-2.977)

O6"-1pz; O4"-1pz Cl2'-2px; Cl2'-3px N1-1py; C2-1py N1-1pz; N14-1pz

79
 ES-PDHOP

88-HOMO-3 (-6.732) 91-HOMO (-5.192) 92-LUMO (-3.701)

O2''-1pz; O4''-1py Cl2'-2pz; Cl2'-3pz N14-1pz; N1-1pz

ES-SHP

69 -HOMO-10 (-8.661) 70 -HOMO-9 (-8.493) 77 -HOMO-2 (-6.767) 79 -HOMO (-6.490) 80 -LUMO (-3.412)
N1-1py C13-1pz; C12-1pz N1-1py; C5-1pz O4''-1pz; O4''-2pz N1-1pz; N14-1pz

80
 Table 1: Structural Parameters
Bond Length (Å) Bond Angle (˚) Dihedral Angle (˚)
Atom Atom Atom Pair
ES- ES- ES- ES-
Pair ES-BA ES-SPH Pair ES-BA ES-BA ES-SHP
PDHOP PDHOP SHP PDHOP
H1'-Cl2' -62.57
1.3591 1.7166 1.3461 Cl2'-H1'-N1 177.73 175.34 177.22 Cl2'-H1'-N1-C2 -69.26 -98.13

38.84
N1-H1' 1.6720 1.1533 1.7244 H1'-N1-C2 114.20 114.37 113.80 H1'-N1-C2-C7 40.05 30.51

9.73
N1-C2 1.4046 1.4096 1.4022 H1'-N1-C8 120.91 116.44 121.25 H1'-N1-C8-C9 9.52 11.40

-178.04
N1-C8 1.3032 1.3136 1.3033 N1-C2-C7 117.58 116.68 117.47 N1-C2-C7-C6 -177.83 -178.29

9.70
C2-C3 1.4077 1.4051 1.4087 C2-C3-C4 120.01 119.49 120.00 C2-N1-C8-C13 9.08 7.559

0.35
C2-C7 1.4066 1.4054 1.4075 C3-C4-C5 120.39 120.37 120.37 C2-C3-C4-C5 0.20 -0.429

-3.29
C3-C4 1.3933 1.3922 1.3929 C5-C6-C7 120.41 120.44 120.40 C3-C2-C7-C6 -3.05 -2.947

1.98
C4-C5 1.3959 1.3970 1.3961 C6-C7-C2 120.06 119.45 120.05 C4-C3-C2-C7 1.94 2.515

2.28
C5-C6 1.3977 1.3971 1.3980 C7-C2-C3 119.32 120.24 119.31 C5-C6-C7-C2 2.038 1.298

-139.06
C6-C7 1.3911 1.3914 1.3906 C8-N1-C2 124.82 128.99 124.90 C7-C2-N1-C8 -137.40 -144.31

81
 0.00
C8-C13 1.4682 1.4566 1.4679 C9-C10-C11 121.11 121.70 120.52 C8-C13-C12-C11 0.00 0.00

1.09
C9-C10 1.3476 1.3480 1.3493 C10-C11-C12 117.05 116.97 117.31 C9-C10-C11-C12 1.39 0.00

-2.48
C10-C11 1.4674 1.4651 1.4660 C11-C12-C13 121.79 121.60 121.91 C10-C11-C12-C13 -2.59 -2.047

C12-C11-N14- -0.99
C11-C12 1.4691 1.4724 1.4688 C12-C13-C8 120.87 120.34 120.72 -0.85 0.00
H15

-180.00
C11-N14 1.2925 1.2906 1.3001 C13-C8-N1 124.94 124.363 125.08 C12-C13-C8-N1 -180 -178.441

C12-C13 1.3472 1.3494 1.3472 N14-C11-C12 124.08 122.797 122.66 C13-C12-C11-N14 178.66 180 178.95

N14-H15 1.0230 1.0386 1.0228 H15-N14-C11 111.97 110.665 110.54

82
 Table 2 :Mulliken's Atomic Charge Density

ES-BA ES-PDHOP ES-SPH

Atom Charge Atom Charge Atom Charge

H1' 0.1804 H1' 0.2589 H1' 0.1740

Cl2' -0.3049 Cl2' -0.6073 Cl2' -0.2849

N1 -0.6056 N1 -0.6007 N1 -0.5955

C2 0.2475 C2 0.2567 C2 0.2482

C3 -0.0978 C3 -0.0945 C3 -0.0979

C4 -0.0960 C4 -0.0986 C4 -0.0960

C5 -0.0772 C5 -0.0718 C5 -0.0760

C6 -0.0924 C6 -0.0939 C6 -0.0919

C7 -0.0915 C7 -0.0896 C7 -0.0909

C8 0.3346 C8 0.3519 C8 0.3301

C9 -0.1055 C9 -0.1059 C9 -0.1167

C10 -0.0895 C10 -0.0696 C10 -0.0924

C11 0.3172 C11 0.3009 C11 0.3281

C12 -0.1060 C12 -0.0897 C12 -0.1079

C13 -0.0927 C13 -0.1017 C13 -0.0898

N14 -0.5900 N14 -0.6363 N14 -0.6310

H15 0.2421 H15 0.3162 H15 0.2474

83
 Table 3: Dipole moment (D)

µx µy µz µTotal

BA 0.9396 -2.9534 0.0000 3.0993

ES-BA -0.1208 7.8225 -0.7469 7.8590

PDHOP -9.0437 1.9199 -3.3802 9.8437

ES-PDHOP 8.1321 2.0091 -0.8563 8.4202

SHP -4.1386 2.8157 -0.0522 5.0059

ES-SHP -5.4426 9.4804 2.4655 11.2062

84
 Table 4: TDDFT

ES-BA ES-PDHOP

Wave Length Oscillatory

Orbital % Contribution Wave Length Oscillatory
(nm) Strength Orbital % Contribution
(nm) Strength
429.4 0.2462 73a →74a 76.82
362.8 0.6504 88a → 92a 69.62

310.5 0.1368 67a → 74a 35.38

ES-SHP
65a → 74a 37.58
293.1 0.3283 Wave Length Oscillatory
Orbital % Contribution
67a → 74a 26.77 (nm) Strength

443.7 0.2555 77a → 80a 77.04

256 0.6363 65a → 74a 34.12

322 0.1362 70a → 80a 40.28

69a → 80a 42.04

299.4 0.3009
70a → 80a 40.64

85
 Table 5: Frontier Molecular Orbital

eV
Electron Electronic chemical Chemical Global QMax
Band Gap Ionisation Electrophilic index EN
affinity potential hardness softness
potential

BA 9.6 8.4 -1.2 -3.6 4.8 0.2 30.4 3.6 0.7

PDHOP 4.3 5.9 1.6 -3.7 2.2 0.5 15.2 3.7 1.7

SHP 5.3 6.7 1.4 -4.1 2.6 0.4 21.9 4.1 1.5

ES- BA 3.5 6.5 3.0 -4.8 1.8 0.6 20.0 4.8 2.7

ES-PDHOP 1.5 5.2 3.7 -4.4 0.7 1.3 7.4 4.4 6.0

ES- SHP 3.1 6.5 3.4 -5.0 1.5 0.6 18.9 5.0 3.2

86
 Table 6: Polarisability (Au)

Axis BA ES-BA PDHOP ES-PDHOP SHP ES-SHP

µZ -1.18×10-15 -0.294 -1.33 -0.337 -0.0206 0.970

-12
αXZ -3.26 -1.51 0.713 22.5 0.148 13.5

-12
αYZ 7.55 12.0 -0.291 -23.5 0.0119 3.70

αZZ 12.7 86.7 34.0 105 29.1 102

βXZZ -0.494 -15.0 112 -218 91.1 -96.0

βYZZ 0397 -16.1 -21.2 95.0 -62.6 -84.9

-09
βZZZ 1.23 -6.48 37.2 -11.5 3.44 -68.9

γZZZZ 248 966 7750 8800 5660 7700

87
 Table 7: Conductance
ES-BA
Mole
Conductance
Fraction of
S/cm 0.6
ES
0.5

1.0000 0.4910

Conductance (S/cm)
0.4

0.3
0.7771 0.1797
0.2

0.6354 0.2491 0.1

0.0
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1
0.5375 0.3020 Mole Fraction of ES

0.4657 0.3579
R y0 a b

Ideal 1.0 -0.1047 0.5957 -

Real 0.9987 0.1946 -0.5059 0.8006

ES-PDHOP

Mole
Conductance
Fraction of
S/cm 0.6

ES 0.5
Conductance (S/cm)

0.4
1.0000 0.4910
0.3

0.2

0.8301 0.1211
0.1

0.0

0.7096 0.1060 0.5 0.6 0.7 0.8

Mole Fraction of ES
0.9 1.0 1.1

0.6196 0.0875
R y0 a b
0.5499 0.0522
Ideal 1.0 -0.4838 0.9748 -

Real 0.9770 1.3866 -4.1602 3.2499

88
 ES-SHP

Mole
Conductance
Fraction of
S/cm 0.6

ES 0.5

0.4
1.0000 0.4910

Conductance (S/cm)
0.3

0.2
0.7919 0.0175
0.1

0.0

0.6555 0.002907
0.6 0.7 0.8 0.9 1.0 1.1

Mole Fraction of ES

R y0 a b

Ideal 1.0 -0.9259 1.4169 -

Real 1.0 3.2007 -9.0049 6.2952

ES-MA

Mole
Conductance
Fraction of
S/cm 0.6
ES
0.5

1.0000 0.4910
Conductance (S/cm)

0.4

0.3

0.8660 0.1660
0.2

0.1
0.7636 0.1092
0.0
0.5 0.6 0.7 0.8 0.9 1.0 1.1

0.6829 0.1011 Mole Fraction of ES

0.6176 0.0745 R y0 a b

Ideal 1.0 -0.5983 1.0893 -

Real 0.9876 2.1565 -6.0143 4.3373

89