Int. J. Electrochem. Sci.

, 7 (2012) 5643 - 5676

International Journal of
ELECTROCHEMICAL
SCIENCE
[Link]

Quantum Chemical Investigations on Quinoline Derivatives as

Effective Corrosion Inhibitors for Mild Steel in Acidic Medium
Eno E. Ebenso1,*, Mwadham M. Kabanda1, Taner Arslan2, Murat Saracoglu3, Fatma Kandemirli4,
Lutendo C. Murulana1, Ashish K. Singh1, Sudhish K. Shukla1, B. Hammouti5, K.F. Khaled6,
M.A. Quraishi7, I.B. Obot8, N.O. Eddy9
1
Department of Chemistry, School of Mathematical & Physical Sciences, North-West
University(Mafikeng Campus), Private Bag X2046, Mmabatho 2735, South Africa
2
Department of Chemistry, Eskisehir Osmangazi University, 26480 Eskisehir, Turkey
3
Faculty of Education, Erciyes University, 38039 Kayseri, Turkey
4
Department of Chemistry, Nigde University, 41000 Nigde, Turkey
5
LCAO-URAC18, Faculte des Sciences, Universite Mohammed Premier, B.P 717, 60000 Oujda,
Morocco
6
Material and Corrosion Laboratory, Chemistry Department, Faculty of Science, Taif University, Taif,
Saudi Arabia
7
Department of Applied Chemistry, Institute Of Technology, Banaras Hindu University, Varanassi
221005, India
8
Department of Chemistry, University of Uyo, PMB 1017, Uyo, Nigeria
9
Department of Chemistry, Ahmadu Bello University, Zaria, Nigeria
*
E-mail: [Link]@[Link]

Received: 1 April 2012 / Accepted: 3 May 2012 / Published: 1 June 2012

The Density Functional Theory (DFT) and ab initio (HF and MP2) calculations were performed on the
quinoline molecule (QL) and its derivatives, namely quinaldine (QLD) and quinaldic acid (QLDA) to
investigate their possible role as corrosion inhibitors for mild steel in acidic medium. Calculations
were done for non-protonated and protonated forms in vacuo and in water. Some quantum chemical
parameters were calculated and discussed in order to provide insight into the reactivity and selectivity
of the molecules. The performance of the different calculation methods were also compared with
available experimental data. The results show that DFT/B3LYP basis set is adequate in describing the
geometry and quantum chemical parameters of the studied systems. Both experimental and theoretical
results established that QLDA has the highest inhibition efficiency. A comparison in the trends of the
quantum chemical parameters in water solution and in vacuo shows minimal influence of the solvent
effects.

Keywords: Reactivity descriptors, DFT, ab initio, solute-solvent, quinoline, quinaldine, quinaldic

acid.
Int. J. Electrochem. Sci., Vol. 7, 2012 5644

1. INTRODUCTION

Mild steel is widely used in many industrial applications such as storage and transportation of
various chemical solutions. However, some substances that are stored or transported in pipes or other
materials made out of mild steel have corrosive properties and in most cases lead to the dissolution of
the metal, resulting in great economic and financial losses for various industries. The dissolution of
mild steel is a result of its direct contact with the corrosive substances (e.g., acidic solutions that are
widely used in industries for various applications such as pickling, acid cleaning, oil well acidizing,
etc. [1]). Several approaches, including anodic and cathodic protection, lubrication, painting and
electroplating, have been proposed to protect the metal from corrosion. Another important method is
the use of corrosion inhibitors [2]. Corrosion inhibitors are substances that adsorb (both physically and
chemically) at the metal-solution interface and in the process block or reduce the contact surface
between the metal and the corrosive materials. In order to achieve its objectives, a corrosion inhibitor
molecule should have specific properties that allow it to adsorb at the metal-solution interface [2].
Such properties are encoded in the molecular structure of the inhibitor e.g. electron density and the
geometry of the molecule. Molecules that have high electron density have a greater tendency to donate
electrons to species that are electron deficient and in the case of metal, the donated electrons could be
accepted into the partially filled or vacant d orbitals resulting in the formation of a coordination bond
(i.e., chemical adsorption) between the metal and the inhibitor. Therefore, molecules containing atoms
with lone pair of electrons (e.g., N, O, S and P heteroatoms), -electrons in triple or conjugated bonds,
aromatic systems, etc are highly utilised as corrosion inhibitors because they have a high electron
density at those specific centres [3]. The geometry of an inhibitor also has an important influence in
determining its adsorbability at the metal-solution interface. Molecules that are planar have a greater
tendency to adsorb at the metal surface than molecule that have less planar geometry [46]. Therefore,
understanding the nature of the molecule provides useful information on its applicability as corrosion
inhibitor. Although the focus of the current work is on the nature of the inhibitor, we hasten to remind
that there are several inter-dependent factors, beside the nature of the inhibitor, which influence the
adsorption of the inhibitor on the metal surface (e.g., the nature of the metal, the environment and the
electrochemical potential at the metal-solution interface). Hence, to understand the adsorption of
inhibitor at the metal-solution interface, it is necessary to have an insight into the effect of all the
factors as much as possible.
In the search for effective corrosion inhibitors in a given class of compounds, having a similar
central moiety and differing only in the substituent’s, it is important to identify the main characterising
features that distinguish a particular compound as a likely effective inhibitor from the rest of the other
compounds. Such studies are usually done using both experimental and quantum chemical approaches.
Quantum chemical calculations have become an effective tool in the analysis and elucidation of many
experimental observations. Moreover, its use in corrosion science as a tool to explain experimental
results is growing, as is noted by the increasing number of published articles that are increasingly
reporting both experimental and quantum chemical results. In the current work, quantum chemical
methods are utilised to study a group of quinoline derivative in order to investigate their possible role
as effective corrosion inhibitors.
Int. J. Electrochem. Sci., Vol. 7, 2012 5645

Quinoline derivatives in general are known to have a variety of pharmacological and biological
activities, such as immunodepresant activity [7], antimalarial activity [8] and antitubecular activity [9].
A few reports have been presented in literature on the use of quinoline and some of its derivatives as
corrosion inhibitors in different media [1015].The present work reports the results of quantum
chemical calculations on quinoline (QL) and two of its derivatives namely quinalidine (QLD) and
quinaldic acid (QLDA) in order to understand their possible role as corrosion inhibitors of mild steel in
hydrochloric acid. Their molecular structures are shown in figure 1 below.

N N CH3 N CO OH
QL QLD QLDA

Figure 1. The molecular structures of the studied quinoline compounds.

These compounds have a pyridine ring (i.e., an aromatic ring containing an N atom) and a
benzene ring fused together. In our previous work on these structures (i.e., QL, QLD and QLDA), we
reported experimental results on their corrosion inhibitory role in hydrochloric acid medium and
concluded that the inhibition efficiency follows the order QLDA > QLD > QL [16]. In the current
work, the quantum chemical results on these compounds are discussed and compared with the
experimental results in order to obtain a better understanding of the molecular features that
distinguishes one compound from the others as a better corrosion inhibitor and to provide supportive
explanations for the observed experimental trends. Moreover, any differences in the results of the
quantum chemical calculations and experimental results are highlighted and discussed.

2. COMPUTATIONAL DETAILS

Different quantum molecular properties may be described better by different computational

methods, depending on the sophistication of the computational approaches. In view of this, three
different computational methods, viz., Density Functional Theory (DFT), Hartree Fock (HF) and
second order Møller–Plesset perturbation theory method (MP2) were selected for the study of the
compounds used as corrosion inhibitors. Although HF does not take into account correlation and
dispersion effects, it provided useful results for comparison with other methods, Moreover, for cases
where HF provided results that are closer to those of sophisticated methods; further study at HF level
was done because it is less computationally expensive. DFT takes into account a part of correlation and
it has been reported to provide fairly good results for the description of various molecular properties
such as the energy of the Highest Occupied Molecular Orbital (HOMO), the energy of the Lowest
Unoccupied Molecular orbital (LUMO), electronegativity (), ionization potential, etc., [17]. In the
present study, DFT in combination with the B3LYP and the BP8 functionals were utilized in order to
Int. J. Electrochem. Sci., Vol. 7, 2012 5646

compare the effect of the different functionals on the calculated molecular properties for the systems
under study. DFT/B3LYP has been widely used in the description of the inhibitor metal surface
mechanism and is also recommended for the study of chemical reactivity and selectivity of molecules
[18, 19].
MP2 takes into account both correlation effects and dispersion effects and its use in the current
study provided good description of molecular properties for which such effects might be predominant.
In this way, the selected methods give wide possibilities for obtaining reasonable estimations of trends
in the molecular properties of the studied molecules. The basis set selected for a particular molecular
calculation provided an idea of the sophistication of the model chemistry (i.e., method plus basis set)
utilised for a particular study. The selection of model chemistry on the other hand is strongly
dependent on the size of the system to be studied, type of calculations to be carried out and available
computational facilities. It is therefore essential to select a model chemistry that does not compromise
the meaningful-ness of the results and at the same time it is not too computationally demanding for the
available facilities. Since the current study is done both in vacuo and in water solution, four basis sets
were selected and considered adequate enough to take into account necessary features of the desired
molecular properties. Calculations at HF level were done using the 6-31G(d,p) basis set; calculations at
MP2 level were done by using both 3-21G and 6-31G (d,p) basis sets; calculations at DFT/B3LYP
were done using the 6-31G(d,p) and 6-31++G(d,p) basis sets and calculations at DFT/BP8 were done
by using the CEP-31G basis set.
Molecular properties, related to the reactivity and selectivity of the compounds, were estimated
following the Koopmans’s theorem relating the energy of the HOMO and the LUMO [20].
Electronegativity is estimated using the following the equation:

  ½ (EHOMO + ELUMO) (1)

Chemical hardness () measures the resistance of an atom to a charge transfer [21], it is
estimated by using the equation:

  ½ (EHOMO – ELUMO) (2)

Global electrophilicity index () is estimated by using the electronegativity and chemical
hardness parameters through the equation:

2
= (3)
2

A high value of electrophilicity describes a good electrophile while a small value of

electrophilicity describes a good nucleophile.
Electron polarizability, also called chemical softness (), describes the capacity of an atom or
group of atoms to receive electrons [21] and is estimated by using the equation:
Int. J. Electrochem. Sci., Vol. 7, 2012 5647

 = 1/  2/(EHOMO – ELUMO) (4)

Electron affinity (A) is related to ELUMO through the equation:

A  – ELUMO (5)

Ionization potential (I) is related to the EHOMO through the equation:

I   EHOMO (6)
The maximum number of electrons transferred (∆Nmax) in a chemical reaction is given by the
equation;


∆Nmax = (7)
2

and on using the I and A terms can be written as

( I  A)
∆Nmax = (8)
2( I  A)

The study in solution considers the bulk solvent effects and are estimated with the polarisable
continuum model (PCM) with its default settings as described in [22] and as implemented in the
Gaussian03 package [23]. The inhibition efficiencies of the quinoline derivatives were obtained
experimentally using the weight loss method [16].

3. RESULTS AND DISCUSSIONS

The calculated quantum chemical descriptors provide trends in the reactivity and selectivity
features of the studied compounds. Calculations were done in vacuo and in water solution and by
considering both the protonated and the non-protonated species. The results of the calculations in
solution provide information that would be more realistic, considering that electrochemical processes
are mostly done in solution.
The results show that QLDA is the most preferred compound as corrosion inhibitor with the
order of inhibition efficiency being QLDA > QL > QLD. A comparison of the protonated and the non-
protonated species show that there are some significant quantum chemical parameter differences
between the protonated and the non-protonated species as a result of difference in electron density
distribution between the protonated and the non-protonated species. The results in solution, however,
are similar to the results in vacuo, both for the protonated and the non-protonated species, probably
due to the lack of significant molecular geometry changes. The difference in the trends between the
theoretical results and experimental results are related to two competing factors; geometry planarity
Int. J. Electrochem. Sci., Vol. 7, 2012 5648

and electron density of the inhibitors, with the electron density factor appearing to be preferred as
evidenced by experimental results.

3.1. Results of the calculations in vacuo for the non-protonated species

QL QLD QLDA

Optimized
structures

HOMO

LUMO

Figure 2. The optimized structures, HOMO and LUMO of the non-protonated inhibitor molecules
(using B3LYP/6-31++G (d, p) results).

The optimised geometries of the non-protonated species are show in figure 2 above together
with the atom numbering utilised throughout this work; the HOMO, the LUMO and the total electron
density of each compound. Table 1 shows the bond length of the CC and CN for the studied
systems. In the absence of experimental results on geometrical parameters of quinoline, the calculated
bond lengths reported in Table 1 are compared with the experimental bond lengths of naphthalene
reported in [24]. The results show that for the C1C2, C4C5, C1C6, C1C7, C8C9 and C2C10
bond lengths, HF and DFT/B3LYP results are closer to experimental results than MP2, which appears
to overestimate the length of the CC bond. A comparison of the C5C6, C7C8 and C9C10 bond
lengths using different calculation methods and those for naphthalene show that HF underestimates the
bond length, but both MP2 and DFT/BP86 overestimates the bond lengths, while DFT/B3LYP results
are closer to the experimental results. In this way, DFT/B3LYP results provide the best estimate for the
geometry of quinoline and its derivatives. Addition of diffuse orbital to DFT/B3LYP does not seem to
Int. J. Electrochem. Sci., Vol. 7, 2012 5649

have a significant influence on the length of the CC bonds or CN bond. Moreover, DFT/B3LYP
results on geometry are in good agreement with the CC and CN bond lengths for quinoline obtained
by using the force field refinement method reported in [25]. Based on these results any further
discussion on the geometry of quinoline and its derivatives (e.g., the geometry of the protonated
species and that of the non-protonated species) will be exclusively based on the DFT/B3LYP results.
The overall geometry of the molecule is better described by taking into account not only the
bond lengths, but also the bond angles and torsion angles of the atoms of the molecule. A comparison
of the geometries of the molecules shows that QL and QLDA are highly planar while, QLD is less
planar because of off-plane orientation of the H atoms of the methyl group.

QL QLD (first orientation) (QLD) (second orientation)

Figure 3. Planarity influencing factor in quinoline (QL) and quinaldine (QLD). The region between
the dotted lines represents the surface of the metal.

Figure 3 shows the two orientations of the QLD molecule compared with the orientation of QL
on the metal surface. Both orientations of QLD do not cover the surface of the metal desirably and
therefore would not result in effective corrosion inhibition; the QL molecule, on the other hand, has
maximum coverage of the surface of the metal and therefore would theoretically be a better corrosion
inhibitor than QLD. Therefore, in terms of adsorbability on the metal surface, the trends, as predicted
by the geometry of the molecules, would most probably be such that QLDA > QL > QLD.
Beside the geometries of the compounds, an analysis of other quantum chemical parameters
provided valuable information on the reactivity and selectivity of quinoline and its derivatives. These
pieces of information were valuable in selecting a suitable compound or compounds (among
compounds of similar structural features) to use as corrosion inhibitor as they inform which molecule
has greater tendency to donate electrons, receive electrons or bind more strongly to the metal surface.
Quantum chemical parameters such as the energy of the Highest Occupied Molecular Orbital (E HOMO)
and the energy of the Lowest Unoccupied Molecular Orbital (ELUMO), the EHOMO – ELUMO energy
difference (E) [EHOMO – ELUMO], the dipole moment (D), the charges on the atoms, the molecular
volume (MV) and sum of the total negative charge (TNC) are often sighted among the most important
quantities that provide information on the reactivity of the systems under consideration. Other
quantities include the global hardness (), global softness (), electronegativity (), chemical potential
() and fraction of transferred electrons (N). The various parameters are collectively reported in Table
2.
The HOMO and the LUMO for the studied molecules are shown in figure 2 together with the
total electron density. In the quinoline molecule, the HOMO and the LUMO are delocalised
throughout the system with the HOMO having the maximum amplitude coefficients on C7 and C10
Int. J. Electrochem. Sci., Vol. 7, 2012 5650

atoms while the LUMO has the maximum amplitude coefficient on C6 and N3. The LUMO on these
centres has an anti-bonding character; the total electron density shows that the negative charge
(indicated in red colour) is strongly localised on the N atom while the rest of the molecule appears to
have a neutral distribution of charges (green colour). The negative charge on the N atom is likely due
to the electron cloud of the lone pair of electrons.
In the QLD, the HOMO and LUMO orbitals are also strongly distributed across the molecule,
with the exception of the CH3 group. As is the case in quinoline, the maximum amplitude of the
HOMO coefficient is on C7 and C10 atoms while the maximum amplitude of the LUMO coefficients
is on C6 and N3. The total electron density of QLD reveals that only the N atom has the highest
negative charge density, which may also be related to the electron cloud of the lone pair of electron on
the N atom. However, in comparison to the QL molecule, the total electron density of the QLD
molecule shows significant distribution of negative charge in the rest of the ring (i.e., there is more
yellow colour in the benzofused heterocyclic ring of QLD than in the benzofused heterocyclic ring of
QL). This phenomenon is the result of the electron donating inductive effect of the CH 3 to the ring,
resulting in the spread of the negative charge to some parts of the benzofused heterocyclic ring
In the quinaldic acid (QLDA), the HOMO is delocalised only on the two rings, with a strong
maximum amplitude coefficient on C6 and C10. The LUMO is distributed not only on the rings but
also on the C atom of the carbonyl group, and has its maximum amplitude on the C6 and N3 atoms.
The total electron density of QLDA reveals that the negative charge is strongly delocalised in two
regions namely in the region between the N atom and the sp3 O of the carboxylic functional group and
in the region ahead of the sp3 O of the carbonyl functional group. This high negative charge density is
also strongly related to the lone pair of electrons of the three heteroatoms (N, sp3 O and sp2 O atoms).
The two regions would readily interact with electrophilic species resulting in the electron rich QLDA
molecule providing electrons to the vacant orbitals of an incoming electron deficient species. The total
electron density of QLDA also reveals that the H atom of the carboxylic functional group is strongly
electron deficient (excess blue colour) and therefore it is most likely to be attacked by electron rich
species. A comparison of the total electron densities for the three molecules shows that QLDA has the
least electron density distributed in the benzofused heterocyclic ring. This phenomenon is a result of
the electron withdrawing effect of the COOH group, which results in the deactivation of the rings.
Collectively, the electron density distribution for the three molecules is such that QLDA >
QLD> QL, suggesting that QLDA would have the greatest tendency to adsorb on the metal-solution
interface while QL would have the least tendency to adsorb onto the metal-solution interface.
The EHOMO informs of the tendency of a molecule to donate electrons to the electron deficient
species. The higher the EHOMO value the greater the tendency to donate electrons. The EHOMO for the
three compounds follow the order; QLD > QL > QLDA which implies that the molecule which has the
highest tendency to donate electrons is QLD. The trend may be explained as follows: QLD has a high
electron density than QL and therefore it is understandable that it would have a greater tendency to
donate electrons than QL. QLDA on the other hand has the highest electron density because of the
presence of O atoms that have lone pair of electrons. However, because O atoms are highly
electronegative, the lone pairs of electrons on the O atoms are tightly held so that the tendency to
donate electrons is minimal. The ELUMO informs of the tendency of a molecule to accept electrons from
Int. J. Electrochem. Sci., Vol. 7, 2012 5651

an electron rich species. The lower the ELUMO value the greater the tendency to accept electrons. The
ELUMO for the three compounds follows the order; QLDA > QL > QLD which implies that QLDA has
the greatest tendency to accept electrons. Three regions in the QLDA molecule are significantly
electron deficient namely the benzene ring (due to the electron withdrawing effect of the carboxylic
functional group), the C and H atoms of the carboxylic functional group (because of the great
electronegativity difference with respect to the O atom attached to both C and H atoms of the
carboxylic group). These high number of electron deficient centres make the QLDA molecule possess
the highest tendency to accept electron. The ring in the QLD molecule is however electron rich
because of the presence of the CH3 group that donates electrons to the benzofused heterocyclic ring,
therefore in relation to the parent compound QL, QLD has a less tendency to accept electrons. E
value informs of the reactivity of the molecular systems. Molecules with the lowest value of E have
the highest tendency to react. The trend for the E values follows the order QLDA > QL > QLD which
suggests that QLDA has the highest reactivity in comparison to the other compounds and would
therefore likely interact strongly with the metal surface. Collectively, the results show that the trend in
the EHOMO, ELUMO and E does not correlate with the trend in the observed inhibition efficiency.
However, both the theoretical and experimental results agree that QLDA has the highest tendency to
interact with the metal surface.
The dipole moment of the molecule gives information on the polarity of the given system.
Molecules that have high dipole moment have a tendency to interact with other molecule through
electrostatic interactions (e.g., dipole-dipole interactions). The dipole moment of a molecule is strongly
determined by the shape of the molecule, size of the molecule and type of atoms constituting the
molecule. The relationship between inhibition efficiencies and dipole moment of similar molecules
have often given results that are not univocal, i.e., in some instances the dipole moment appears to
increase with increasing inhibition efficiencies [26] while in other systems the dipole moment appears
to decrease with increase in the inhibition efficiencies of the inhibitors [27]. The results of the dipole
moment for the QL, QLD and QLDA are reported in Table 2. The dipole moment of QL has been
earlier reported experimentally in literature [26]. A comparison of the experimentally determined
dipole moment and the theoretical results obtained from this work show that ab initio HF method gives
results that are much closer to experimental results; DFT underestimates the magnitude of the dipole
moment while MP2 overestimates the magnitude of the dipole moment. Overall, the trend in the dipole
moment follows the order; QLDA > QL > QLD, which is not in agreement with trends in the
experimental inhibition efficiencies of the inhibitors earlier reported in literature[16].
A comparison of the sum of the total negative charge (TNC) across structures shows that it
follows the order; QLDA > QLD > QL. This result is consistent with the analysis of the electron
density that showed that the electron density is highest for QLDA and lowest for QL. The trend in the
total negative charge is also in line with the trend in the experimentally obtained inhibition efficiencies
of the inhibitors.
The partial charges on the individual atoms in a molecule also indicate the reactive centres for a
particular inhibitor. Atoms with the highest negative charge are considered to have an electron donor
role when interacting with metal surfaces. The Mulliken atomic charges for the heteroatoms of the
quinoline derivatives are reported in table 1 and show that N3 has the highest negative charge with
Int. J. Electrochem. Sci., Vol. 7, 2012 5652

MP2/3-21G, MP2/6-31G(d,p), HF/6-31G(d,p) and DFT/6-31G(d,p) methods. Moreover, the negative

charge on the N atom increases across the structures following the order; QLDA < QL < QLD. This
result is consistent with the fact that the electron withdrawing effect of the COOH group in QLDA
decreases the negative charge on the N atom in the ring while the electron donating role of the CH3
increases the negative charge on the N atom in QLD. The negative charge on the O atoms of QLDA
shows that it is highest on the sp2 O atom than on the sp3 O atom, which suggests greater electron
donor role of the sp2 O than the sp3 O atom. In view of the above results, QLDA has greater tendency
to adsorb on the metal surface because it has three highly negative charged centres while QL is
preferentially the molecule with the least negative charge.
The fraction of electron transferred follows the order; QLDA < QL < QLD. This is
understandable considering that QLDA has the least number of electrons that are loosely bound
(because the high electronegativity of O atoms causes the electron density to be tightly bound to the
molecule) while QLD has the highest electron density (due to the electron donating effect of the CH 3
group).
The local selectivity descriptor of an inhibitor also indicates the centers in the molecule on
which certain types of relativities are most likely to occur. These descriptors are often described in
terms of the condensed Fukui functions. Fukui functions provide information related to the atoms in a
molecule that have a higher tendency to either loose (i.e., a site that is susceptible to an electrophilic
attack) or accept (i.e., a site that is susceptible to a nucleophilic attack) an electron or pair of electrons.
In most cases, the Fukui functions for the electron rich centers (i.e., atoms susceptible to electrophilic
attack) and electron deficient centers (i.e., atoms that are susceptible to nucleophilic attack) are
calculated using the finite difference approximation approach as follows [28];

f + = q(N+1)  qN (9)

f  = qN  q(N1) (10)

where q(N+1), q and q(N1) are the charges of the atoms on the systems with N+1, N and N1
electrons respectively. The preferred site for nucleophilic attack is the atom (or region) in the molecule
where f + has the highest value while the site for electrophilic attack is the atom (or region) in the
molecule where the value of f  is the highest. The calculated values of the Fukui functions for the non-
hydrogen atoms in the three studied molecules are reported in Table 3 and Table 4 for f  and f +
respectively, for the non-protonated species. The preferred site for nucleophilic attack is the C6 atom
for both QL and QLD while the preferred site for nucleophilic attack in QLDA is N3. The electrophilic
attack (shown by the highest value of f ) would preferably occur at the C7 and C10 atoms.

3.2. Results of the calculations in vacuo for the protonated species

The inhibitor protects the metal surface by blocking or reducing its interaction in acidic
medium. However, because of the presence of heteroatom with a number of lone pair of electrons, the
Int. J. Electrochem. Sci., Vol. 7, 2012 5653

interaction between the acidic medium and the inhibitor may result in the protonation of the inhibitor
at the heteroatom centers. In such cases, it is interesting to investigate the characteristics of the
corrosion inhibitor in the protonated form so as to compare it with the non-protonated form. Such a
comparison provides information on the preferred form of the inhibitor to interact with the metal
surface.
In the quinoline derivatives considered in this work, the N atom is the only heteroatom that is
common to all the systems, therefore, for the purpose of comparison of trends across structures, it is
meaningful to investigate only the protonation on the N atom. The charges on the heteroatoms and the
bond distances for the protonated species are reported in Table 5. The results show that, in comparison
to the results of the non-protonated species, the charge (e) on the N atom obtained using the MP2/3-
21G, MP2/6-31G(d,p), HF/6-31G(d,p) and DFT/6-31G(d,p) methods is higher in the protonated form
than in the non-protonated form; the charge (e) on the O atoms of QLDA decreases by 0.066 for DFT,
0.093 for HF and 0.100 for MP2 for sp2 O atom and increases by 0.014 for DFT, 0.043 for HF and
0.05 for MP2 for the sp3 O atom with respect to the non-protonated form.

Protonated structure HOMO LUMO total density

Figure 4. The optimised structures, HOMO, LUMO and the total electron density for the protonated
inhibitor molecules (using B3LYP/6-31++G (d,p) results in vacuo).

A comparison of the bond lengths using the DFT/B3LYP method shows that the CC bond
lengths (Å) are often longer in the non-protonated form than in the protonated form (by  0.0040.024
Å) while the C2N3 and N3C4 bond lengths (Å) are consistently shorter in the non-protonated form
Int. J. Electrochem. Sci., Vol. 7, 2012 5654

than in the protonated form (by 0.011 and 0.021 for QL, 0.014 and 0.042 for QLD and 0.011 and 0.023
for QLDA respectively).The HOMO and LUMO of the protonated species are shown in figure 4 while
the quantum chemical parameters related to the reactivity of the protonated species are reported in
Table 4. Like in the non-protonated species, the HOMO is strongly localized (i.e., it has a high
amplitude) on C7 and C10 atoms for all the species. The LUMO on the other hand has the highest
amplitude on C4 and C6. The electron density mapped onto the potential surface for the three
molecules show that electron deficient regions (blue color) dominate much of the molecule and is
strongly localized in the region ahead of the N atoms. This phenomenon is a result of the high
electronegative charge of the N atom that leaves the H atom attached to it highly electron deficient.
The electron deficient regions are more spread in QLD than in QL and are highest in QLDA, probably
because of the presence of two proton species, one on the N atom and the other on the sp3 O atom.
Overall, the results reveal that the protonated species are electron deficient and therefore have a less
tendency to donate electrons to the electron deficient species as compared to the non-protonated
species.
The Mulliken charges obtained using DFT/B3LYP/6-31++G (d,p) are significantly different
from the results of other methods. This result is consistent with the fact that Mulliken atomic charges
are strongly basis-set sensitive and in most instances tend to become unphysical when large basis sets
with diffuse functions are employed [27]. The Mulliken atomic charges on the N atom obtained by
using the DFT/BP86/CEP-31G method are also not realistic (Table 5).
A comparison of the quantum chemical parameters of the protonated species (Table 6) and
those of the non-protonated species (Table 2) show similarity for the two forms. For instance, in
protonated and non-protonated form, the order of the EHOMO is such that QLDA > QLD > QL; the
order of the ELUMO is such that QLDA > QL > QLD. A comparison of the individual values of the
EHOMO, ELUMO and E show that EHOMO for the protonated form is lower than for the non-protonated
form, which suggests that the non-protonated form has greater tendency to donate electron pair than
the protonated form; ELUMO has lower values in the protonated form than in the non-protonated form,
implying that the protonated form has a greater tendency to accept electrons than the non-protonated
species; E is smaller for the protonated form than for the non-protonated form, meaning that the
protonated form has greater reactivity than the non-protonated form (i.e., the protonated form has a
greater tendency to adsorb on the metal surface than the non-protonated form). These results are in
agreement with the analysis of the electron density mapped on the potential surface for the non-
protonated and the protonated species.
The dipole moment is higher for the protonated species than for the non-protonated species (for
the HF and DFT results) suggesting that dipole-dipole interactions are more predominant in the
interaction between the metal surface and the protonated form than in the interaction between the metal
surface and the non-protonated form. The sum of the negative charges appears to be higher for the
protonated form than for the non-protonated form obtained using HF and MP2 methods. DFT results
do not give a specific trend on the sum of the negative charges.
Tables 7 and 8 show the f + and the f  values respectively for the condensed Fukui functions of
the protonated species. f + has the highest values for the C4 and C6 atoms, indicating that these are the
preferred centers for a nucleophilic attack on the protonated species. This result is slightly different
Int. J. Electrochem. Sci., Vol. 7, 2012 5655

from the results obtained for the non-protonated species where it was shown that the preference for
nucleophilic attack was on N3 and C6. The highest f  values correspond to the C7 and C10 atoms;
these atoms would therefore be the preferred centers for an electrophilic attack.

3.3. Results of the calculations on the quinoline derivatives in water solution.

Tables 9 and 10 show the CC and CN bond lengths for the non-protonated and protonated
species respectively. The CC and CN bond lengths do not change substantially (the changes are less
than 0.003Å) with respect to the results in vacuo which suggest that the solvent has minimal effects on
the geometry of the inhibitors. The minimal geometric change is the result of the absence of significant
rotatable single bonds in the molecules of QL, QLD and QLDA.
Tables 11 and 12 show the quantum chemical parameters for the non-protonated and the
protonated species respectively. These parameters give information on the chemical reactivity of the
studied molecules in solution. Trends in the quantum chemical parameters are similar for the results in
vacuo and in water solution. EHOMO, ELUMO and E show only a slight increase (absolute values) with
respect to the results in vacuo. The dipole moment is higher in water solution than in vacuo, which is
also a result of the polarization of the solute (inhibitors) by the solvent, resulting in an increased charge
separation in the solute. The Mulliken charge on the individual atoms (table 9 for the non-protonated
and table 10 for the protonated species) is higher in solution than in vacuo. This observation is also a
consequence of the increased charge polarization induced by the solvent. The total negative charge of
the molecule is higher in water solution than in vacuo.
The condensed Fukui functions for the inhibitor are reported in tables 13 and 14 for the non-
protonated and tables 15 and 16 for the protonated species. The results show similar trends which
suggests that the centers for the electrophilic and nucleophilic attack are the same in vacuo and in
water solution.
The similarity in the trends in the geometry and other quantum chemical parameters in vacuo
and in water solution is attributed to the fact that the geometry of the molecules do not change
significantly between the results in vacuo and the results in water solution, because of the absence of
rotatable single bonds. Significant differences in some quantum chemical parameters (e.g., the dipole
moment) between the results in vacuo and in water solution arise mainly due to the effect of the
solvent on those properties.

3.4. The adsorption of the quinoline derivatives on the metal surface

The binding capability of the metal on the inhibitor depends strongly on the electronic charge
of the active site [29]. The Mulliken atomic charges of the non-protonated species show that the N
atom, in all the calculated compounds, has the highest negative charge. Based on these results, each
inhibitor molecule was allowed to interact with the Fe metal at the N atom. The interaction energy
between the inhibitor and the metal was then estimated as the difference between the energy of the
Int. J. Electrochem. Sci., Vol. 7, 2012 5656

complex (EFe-X) and the sum of the energy of the isolated inhibitor and isolated Fe atom (EX + EFe)
resulting in the equation;

Einteration = EFe.-X  (EX + EFe) (9)

The interaction energy between the metal and the inhibitor is reported in table 17 and show that
the trend follows the order; QLDA-Fe > QL-Fe > QLD-Fe, which confirm that QLDA has the
strongest interaction with the metal surface (i.e., it is the most efficient inhibitor). These results are
also supported by the comparison of the N3-Fe18 bond distances (reported in Table 1) that show that
QLDA-Fe has the shortest N3-Fe18 bond distance (therefore stronger interactions between QLDA and
the Fe atom) while QLD-Fe has the longest N3-F18 bond distance. Shorter bond distance implies
stronger interactions while longer bond distance implies weaker interactions between concerned
species. Both results (the interaction energy and the bond distances), therefore imply that QLDA bind
strongly to the metal surface, resulting in a stronger adsorption on the metal surface.

QL (Fe-N3) HOMO LUMO total charge densıty

QLD (Fe-N3) HOMO LUMO total charge densıty

QLDA (Fe-N3) HOMO LUMO total charge densıty

Figure 5. The optimized structures, HOMO, LUMO of Fe–inhibitor complexes and total charge
density (using DFT/B3LYP/6-31++G (d, p) results in vacuo).
Int. J. Electrochem. Sci., Vol. 7, 2012 5657

Figure 5 shows the HOMO, the LUMO and the total electron density for the metal-inhibitor
complexes. Both QL and QLD have the HOMO orbital strongly localized on the Fe ion. The electron
density potential surface shows that there is a high negative charge (indicated by the red color) on the
Fe ion (or on the Fe-inhibitor bond) than in the rest of the molecule. In fact, the electron density in this
region (i.e., near the N3 atom) is higher than in the individual QL and QLD molecules, which indicates
that the interaction between the inhibitor and the metal surface results in increased reactivity (i.e., the
interaction does not necessary lead to stability). The HOMO and LUMO of the QLDA-Fe complex are
delocalized throughout the molecule. The total electron density reveals that there is complete negative
charge depletion on the N atom and the sp3 O atom as well as on the Fe ion. Moreover, the charge
density on the two rings appears more neutral than in the QL and QLD molecules, suggesting that
QLDA-Fe complex is the least reactive (i.e. the interaction between QLDA and the Fe ion results in
the most stable system). This observation is strengthened by the analysis of the E values that show
that QLDA-Fe has the highest E value and is therefore the least reactive complex. All these results
point to the fact that the interaction between QLDA and the metal surface give rise to the strongest
adsorption on the metal surface which is also in agreement with experimental results that show that
QLDA has the highest inhibition efficiency.
Both experimental and theoretical results point to the fact that QLDA has the highest inhibition
efficiency. However, theoretical results differ from experimental results on the preference of inhibition
efficiency of QLD and QL, with theoretical results showing that QL would be a better inhibitor than
QLD and experimental results showing the opposite. There are two competing factors in the two
structures that should be considered; planarity and electron density. QL is more planar than QLD
because the methyl hydrogen atoms do not lie on the plane of the benzofused heterocyclic ring of
QLD, resulting in a less planar geometry for the overall molecule. As a consequence, when the QLD
molecule is placed on the metal surface, a part of it that is closer to the methyl group would not lie flat
on the surface (i.e., there would be an angle between the metal surface and the inhibitor), which in
principle should result in reduced inhibition efficiency and this would agree with predicted results.
However, despite the fact that QLD is less planar than QL, it has a higher electron density than QL.
Since a higher electron density molecule leads to greater inhibition efficiency, QLD has a greater
tendency to donate electrons than QL and therefore its absorbability on the metal surface (and
therefore its inhibitor efficiency) is greater than that of QL, which agrees with experimentally
determined inhibition efficiency trends. In this case, therefore, experimental results have provided
decisive information as to which of these two factors (planarity and electron density) pre-dominates
the other.

4. CONCLUSION

The results of DFT and ab initio HF and MP2 calculations on quinoline (QL), quinaldine
(QLD) and quinalic acid (QLDA) have been presented in vacuo and in water solution, taking into
account both the non-protonated and protonated species. The results of the calculated molecular
Int. J. Electrochem. Sci., Vol. 7, 2012 5658

properties show interesting patterns across structures, across media and on the protonated and non-
protonated species. The HOMO, LUMO, condensed Fukui functions and charges on the atoms predict
similar centre that are preferably attacked by nucleophilic or electrophilic species. A comparison of the
results in vacuo and in water solution shows that trends in the molecular properties across structures
are similar, which may be related to the planar geometry of the studied systems (i.e., the geometry of
the molecules are not significantly different in vacuo and in water solution). However, some
parameters (e.g., charges on the atoms and dipole moment) are strongly influenced by the solute-
solvent interactions
A comparison of the protonated species and the non-protonated species show that the
protonated species are more electron deficient than the non-protonated species. However the E values
suggest that protonated species have greater tendency to interact with the metal surface. Quantum
chemical calculations on the Fe-inhibitor complex also reveal that QLDA has a tendency to form the
most stable complex and therefore as an inhibitor has the highest tendency to adsorb strongly onto the
metal surface.
A comparison of the different utilized quantum chemical methods show that DFT/B3LYP gave
results that are more realistic and in the case of the geometry of the conformers, DFT/B3LYP results
are closer to experimental data. MP2 results appear to overestimate the magnitude of the bond length
while HF appears to underestimate the magnitude of the bond lengths.

ACKNOWLEDGEMENTS
M. M. Kabanda, A. K. Singh and S. K. Shukla are grateful to the North-West University for granting
them Postdoctoral Fellowships enabling them to participate in this work. E.E. Ebenso thanks the
National Research Foundation (NRF) of South Africa for funding.

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Int. J. Electrochem. Sci., Vol. 7, 2012 5660

Table 1. The calculated Mulliken charges (e) for selected atoms and bond distances (Ǻ) for non-protonated compounds.
Method Net atomic charge Bond Distance
and
Molecule
N3 O12 O13 Fe18 C1-C2 C2-N3 N3-C4 C4-C5 C5-C6 C1-C6 C1-C7 C7-C8 C8-C9 C9-C10 C2-C10 C4-C11 C11-O12 C11-13 N3-Fe18

MP2/3-21G
QL -0.688 - - - 1.436 1.396 1.345 1.428 1.385 1.431 1.431 1.386 1.430 1.386 1.427 - - - -
QLD -0.786 - - - 1.434 1.396 1.346 1.433 1.382 1.432 1.430 1.387 1.429 1.386 1.427 1.522 - - -
QLDA -0.730 -0.625 -0.703 - 1.438 1.393 1.342 1.425 1.383 1.431 1.430 1.387 1.430 1.385 1.428 1.499 1.243 1.382 -

MP2/6-31G(d,p)
QL -0.570 - - - 1.442 1.399 1.350 1.432 1.392 1.435 1.436 1.394 1.434 1.394 1.431 - - - -
QLD -0.616 - - - 1.440 1.399 1.352 1.439 1.390 1.435 1.434 1.394 1.433 1.394 1.430 1.517 - - -
QLDA -0.537 -0.573 -0.707 - 1.443 1.394 1.351 1.433 1.391 1.433 1.434 1.394 1.434 1.393 1.431 1.498 1.257 1.388 -

RHF/ 6-31G(d.p)
QL -0.587 - - - 1.407 1.356 1.292 1.417 1.356 1.417 1.419 1.358 1.418 1.358 1.419 - - - -
QLD -0.631 - - - 1.404 1.359 1.292 1.428 1.352 1.420 1.417 1.359 1.415 1.360 1.417 1.506 - - -
QLDA -0.582 -0.584 -0.601 - 1.407 1.352 1.292 1.417 1.356 1.416 1.419 1.357 1.419 1.357 1.420 1.502 1.191 1.318 -

B3LYP/6-31G(d.p)
QL -0.506 - - - 1.432 1.367 1.318 1.418 1.374 1.418 1.420 1.376 1.417 1.377 1.420 - - - -
QLD -0.554 - - - 1.430 1.367 1.320 1.427 1.371 1.419 1.418 1.377 1.416 1.377 1.419 1.508 - - -
QLDA -0.554 -0.480 -0.487 - 1.434 1.361 1.320 1.420 1.373 1.418 1.419 1.377 1.418 1.376 1.421 1.501 1.216 1.346 -

B3LYP/6-31G ++(d.p)
QL -0.130 - - - 1.433 1.367 1.319 1.420 1.376 1.419 1.421 1.378 1.419 1.378 1.421 - - - -
QLD -0.145 - - - 1.431 1.368 1.321 1.429 1.373 1.420 1.420 1.379 1.418 1.379 1.420 1.509 - - -
QLDA -0.159 -0.493 -0.411 - 1.434 1.361 1.320 1.422 1.374 1.419 1.420 1.378 1.420 1.377 1.422 1.502 1.218 1.347 -

BP86/CEP-31G
QL 0.607 - - - 1.461 1.382 1.338 1.445 1.404 1.441 1.444 1.407 1.442 1.408 1.444 - - - -
QLD 0.685 - - - 1.459 1.382 1.341 1.452 1.401 1.442 1.443 1.408 1.441 1.409 1.443 1.527 - - -
QLDA 0.735 -0.058 -0.141 - 1.462 1.376 1.340 1.445 1.402 1.441 1.443 1.407 1.443 1.407 1.445 1.522 1.240 1.370 -

B3LYP/6-31G ++(d.p) (Fe-Complex)

QL -0.153 - - -0.002 1.431 1.391 1.341 1.406 1.377 1.418 1.422 1.377 1.416 1.380 1.416 - - - 1.871
QLD -0.144 - - -0.217 1.428 1.397 1.346 1.417 1.372 1.418 1.420 1.378 1.414 1.381 1.416 1.507 - - 1.883
QLDA -0.186 -0.496 -0.482 0.168 1.425 1.401 1.390 1.414 1.369 1.435 1.414 1.386 1.408 1.387 1.408 1.432 1.216 1.433 1.779
 Int. J. Electrochem. Sci., Vol. 7, 2012 5661

Table 2. The calculated quantum chemical parametersa for non- protonated compounds in vacuo.

Method EHOMO (eV) ELUMO (eV) ∆E (eV) dipole molecular sum of the global Softness chemical electronegativity fraction of
and molecule moment volume total hardness  (eV-1) potential  (eV) electrons
µ (D) MV negative  (eV) Pi (eV) transferred
(cm3/mol) charge ∆N (e)
TNC (e)

MP2/3-21G
QL -8.41 2.11 10.52 2.309 88.480 -2.148 5.260 0.190 -3.150 3.150 0.366
QLD -8.33 2.25 10.58 2.006 101.864 -2.765 5.290 0.189 -3.040 3.040 0.374
QLDA -8.72 1.35 10.07 3.215 125.567 -3.318 5.035 0.199 -3.685 3.685 0.329

MP2/6-31G(d,p)
QL -8.30 2.02 10.32 2.547 132.422 -1.737 5.160 0.194 -3.140 3.140 0.374
QLD -8.21 2.16 10.37 2.255 121.916 -2.272 5.185 0.193 -3.025 3.025 0.383
QLDA -8.66 1.11 9.77 3.455 114.953 -2.901 4.885 0.205 -3.775 3.775 0.330

RHF/ 6-31G(d.p)
QL -8.41 2.43 10.84 2.231 113.487 -1.478 5.420 0.185 -2.990 2.990 0.370
QLD -8.32 2.58 10.90 1.983 96.671 -1.878 5.450 0.183 -2.870 2.870 0.379
QLDA -8.67 1.79 10.46 2.231 123.138 -2.556 5.230 0.191 -3.440 3.440 0.340

B3LYP/6-31G(d.p)
QL -6.30 -1.40 4.90 2.030 103.193 -1.196 2.450 0.408 -3.850 3.850 0.643
QLD -6.20 -1.25 4.95 1.710 116.591 -1.534 2.475 0.404 -3.725 3.725 0.662
QLDA -6.56 -1.98 4.58 2.847 134.400 -2.078 2.290 0.437 -4.270 4.270 0.596

B3LYP/6-31G
++(d.p)
QL -6.59 -1.77 4.82 2.180 96.484 -2.746 2.410 0.415 -4.180 4.180 0.585
QLD -6.48 -1.60 4.88 1.873 121.233 -3.342 2.440 0.410 -4.040 4.040 0.607
QLDA -6.86 -2.36 4.50 2.912 132.993 -4.075 2.250 0.444 -4.610 4.610 0.531

BP86/CEP-31G
QL -5.76 -2.42 3.34 2.078 83.767 -2.468 1.670 0.599 -4.090 4.090 0.871
QLD -5.64 -2.26 3.38 1.725 116.338 -2.568 1.690 0.592 -3.950 3.950 0.902
QLDA -6.05 -2.99 3.06 2.750 116.976 -2.642 1.530 0.654 -4.520 4.520 0.810

a
µ is the dipole moment, MV is the Molecular Volume, TNC is the sum of the total negative charge,  is the global hardness,  is the global softness,  is the chemical potential,  is the
electronegativity and ∆N is the fraction of the electrons transferred
Int. J. Electrochem. Sci., Vol. 7, 2012 5662

Table 3. The calculated condensed Fukui functions for the electrophilic attack (f ) for the non-protonated compounds.

Method and Molecule Atom of interest

C2 N3 C4 C5 C6 C7 C8 C9 C10

MP2/3-21G
QL  12.09 4.26 7.47 11.28 22.57 10.07 8.28 23.09
QLD 2.01 12.85 5.98 4.72 10.31 21.68 12.84 5.75 23.03
QLDA  10.53 2.76 10.13 11.64 23.07 7.87 10.26 22.57

MP2/6-31G
QL 1.03 11.98 3.85 7.44 10.91 22.88 10.11 8.38 23.32
QLD 2.44 12.76 5.59 4.54 9.87 21.95 13.08 5.69 23.29
QLDA 4.38 10.30 2.47 10.16 11.32 23.41 7.80 10.44 22.71

RHF/ 6-31G(d.p)
QL 1.91 10.02 3.90 6.50 9.70 23.36 12.04 8.12 23.94
QLD 5.05 10.41 6.72 2.54 8.05 21.54 16.96 3.97 22.80
QLDA  8.90 2.23 9.57 10.19 23.69 9.05 10.76 23.47

B3LYP/6-31G(d.p)
QL 1.35 10.53 3.56 7.43 10.39 23.60 9.78 8.66 23.96
QLD 2.44 11.40 5.07 4.81 9.62 22.59 12.17 6.40 24.08
QLDA 1.06 9.51 2.65 8.98 10.40 23.90 8.72 9.57 23.67

B3LYP/6-31G ++(d.p)

QL 1.22 10.40 3.33 7.49 10.28 23.81 9.76 8.65 24.31

QLD  11.24 4.69 5.04 9.43 22.80 12.23 6.36 24.28
QLDA  9.22 2.21 9.37 10.32 24.17 8.50 9.75 23.91

BP86/CEP-31G
QL 1.35 9.99 3.33 7.66 9.88 24.07 9.47 8.88 24.48
QLD 2.27 10.89 4.72 5.23 9.15 23.08 11.60 6.79 24.71
QLDA 1.05 8.89 2.34 9.48 9.81 24.34 8.29 9.87 24.11

B3LYP/6-31G ++(d.p)
QL  18.82  3.01  2.36   
QLD  19.62 3.12  3.60 1.62  3.09 
QLDA 3.27 2.72 14.39 1.15 14.09 1.96   
Int. J. Electrochem. Sci., Vol. 7, 2012 5663

Table 4. The calculated condensed Fukui functions for the nucleophilic attack (f +) for the non-protonated compounds.
Method and Molecule Atom of interest
N3 C4 C5 C6 C7 C8 C9 C10

MP2/3-21G
QL 16.07 8.83 8.98 22.49 14.81 5.91 8.11 14.50
QLD 14.59 7.80 10.44 22.31 15.36 5.17 8.90 14.56
QLDA 20.42 14.89 14.58 7.78 9.92 1.81 10.93

MP2/6-31G(d,p)
QL 16.15 9.81 8.80 23.20 14.16 5.71 7.88 13.69
QLD 14.49 8.49 10.53 23.18 14.77 4.82 8.85 13.70
QLDA 20.44 15.46 13.23 6.38 9.66 1.35 9.69

RHF/ 6-31G(d.p)
QL 13.72 9.87 9.80 22.28 14.10 6.07 8.59 13.74
QLD 12.04 8.23 11.88 22.14 22.14 4.97 9.77 13.83
QLDA 17.53 16.87 1.11 15.26 15.26 10.26 2.37 10.57

B3LYP/6-31G(d.p)
QL 16.22 10.67 8.51 22.38 13.48 6.28 7.44 13.22
QLD 14.76 9.36 10.19 22.09 14.09 5.61 8.12 13.33
QLDA 19.18 15.13 14.55 7.16 9.18 2.39 10.42

B3LYP/6-31G ++(d.p)
QL 15.00 11.25 10.28 21.55 12.89 6.59 7.52 13.52
QLD 13.76 9.81 11.51 22.02 13.72 5.75 8.53 13.38
QLDA 18.44 15.91 14.44 6.35 9.54 2.17 10.61

BP86/CEP-31G
QL 15.92 10.75 8.64 22.63 13.23 6.31 7.31 13.29
QLD 14.30 8.99 10.75 22.36 14.03 5.45 8.21 13.34
QLDA 18.85 14.84 14.24 6.56 9.09 2.36 10.55

B3LYP/6-31G ++(d.p)
QL 14.98 13.56 7.02 21.68 10.05 4.97 7.04 9.35
QLD 14.73 11.73 7.94 22.50 10.44 4.28 7.70 8.96
QLDA 14.82 5.42 3.71 2.41 6.42 5.51
Int. J. Electrochem. Sci., Vol. 7, 2012 5664

Table 5. The calculated Mulliken charges (e) for selected atoms and bond distances (Ǻ) for protonated compounds.
Method Net atomic charge Bond Distance
and
Molecule
N3 O12 O13 C1-C2 C2-N3 N3-C4 C4-C5 C5-C6 C1-C6 C1-C7 C7-C8 C8-C9 C9-C10 C2-C10 C4-C11 C11-O12 C11-O13

MP2/3-21G
QL-P -1.001 - - 1.437 1.389 1.354 1.407 1.393 1.424 1.433 1.385 1.432 1.385 1.423 - - -
QLD-P -0.999 - - 1.432 1.394 1.352 1.416 1.387 1.427 1.431 1.386 1.431 1.387 1.422 1.515 - -
QLDA-P -1.001 -0.518 -0.691 1.442 1.384 1.350 1.405 1.391 1.427 1.431 1.386 1.432 1.386 1.423 1.501 1.233 1.385
QLDA-2P -0.988 -0.588 -0.609 1.461 1.379 1.368 1.411 1.395 1.424 1.424 1.391 1.436 1.387 1.423 1.462 1.305 1.316

MP2/6-31G
QL-P -0.992 - - 1.442 1.393 1.357 1.413 1.399 1.429 1.437 1.392 1.437 1.393 1.427 - - -
QLD-P -1.056 - - 1.437 1.397 1.360 1.421 1.395 1.430 1.435 1.393 1.435 1.394 1.426 1.511 - -
QLDA-P -1.038 -0.473 -0.757 1.446 1.387 1.360 1.416 1.398 1.430 1.435 1.393 1.437 1.392 1.428 1.499 1.245 1.390
QLDA-2P -1.046 -0.575 -0.610 1.465 1.382 1.376 1.423 1.400 1.430 1.427 1.399 1.441 1.394 1.427 1.458 1.315 1.326

RHF/ 6-31G(d.p)
QL-P -0.738 - - 1.405 1.368 1.320 1.385 1.374 1.409 1.419 1.358 1.416 1.363 1.404 - - -
QLD-P -0.793 - - 1.400 1.375 1.321 1.401 1.365 1.416 1.415 1.361 1.412 1.366 1.402 1.499 - -
QLDA-P -0.790 -0.491 -0.644 1.409 1.360 1.324 1.381 1.378 1.404 1.422 1.355 1.420 1.361 1.408 1.509 1.176 1.317
QLDA-2P -0.793 -0.504 -0.541 1.438 1.342 1.352 1.366 1.404 1.380 1.433 1.348 1.434 1.358 1.410 1.467 1.258 1.264

B3LYP/6-31G(d.p)
QL-P -0.550 - - 1.429 1.378 1.339 1.394 1.386 1.414 1.420 1.376 1.417 1.380 1.407 - - -
QLD-P -0.604 - - 1.424 1.381 1.342 1.407 1.380 1.416 1.418 1.378 1.415 1.382 1.405 1.496 - -
QLDA-P -0.627 -0.414 -0.501 1.432 1.372 1.343 1.395 1.386 1.413 1.420 1.376 1.419 1.379 1.408 1.504 1.203 1.345
QLDA-2P -0.638 -0.306 -0.417 1.454 1.361 1.362 1.397 1.395 1.404 1.419 1.376 1.429 1.377 1.411 1.456 1.285 1.293

B3LYP/6-31G ++(d.p)
QL-P -0.129 - - 1.430 1.379 1.340 1.395 1.387 1.415 1.422 1.377 1.418 1.382 1.408 - - -
QLD-P -0.135 - - 1.425 1.383 1.343 1.408 1.381 1.418 1.420 1.379 1.416 1.383 1.407 1.497 - -
QLDA-P -0.163 -0.402 -0.475 1.433 1.372 1.344 1.396 1.387 1.413 1.421 1.377 1.420 1.380 1.410 1.504 1.204 1.347
QLDA-2P -0.130 -0.364 -0.373 1.455 1.361 1.362 1.398 1.395 1.405 1.420 1.377 1.430 1.378 1.412 1.456 1.286 1.294

BP86/CEP-31G
QL-P 0.548 - - 1.456 1.394 1.357 1.421 1.414 1.437 1.444 1.406 1.442 1.410 1.431 - - -
QLD-P 0.634 - - 1.451 1.397 1.361 1.433 1.407 1.439 1.443 1.407 1.441 1.411 1.430 1.514 - -
QLDA-P 0.640 0.019 -0.202 1.459 1.389 1.361 1.422 1.412 1.437 1.444 1.406 1.443 1.409 1.432 1.523 1.225 1.370
QLDA-2P 0.598 -0.046 -0.087 1.479 1.379 1.378 1.427 1.417 1.431 1.440 1.407 1.453 1.407 1.435 1.475 1.309 1.317
Int. J. Electrochem. Sci., Vol. 7, 2012 5665

Table 6. The calculated quantum chemical parametersa for protonated compounds.

Method and EHOMO (eV) ELUMO (eV) ∆E (eV) Dipole Molecular sum of the Global Softness Chemical Electronegativit ∆N (e)
Molecule moment volume total hardness  (eV-1) potential y fraction of
µ (D) MV negative  (eV) Pi (eV)  (eV) electrons
(cm3/mol) charge transferred
TNC (e)

MP2/3-21G
QL-P -13.24 -3.47 9.77 3.499 97.524 -2.233 4.885 0.205 -8.355 8.355 -0.139
QLD-P -13.06 -3.12 9.94 3.029 103.093 -3.053 4.970 0.201 -8.090 8.090 -0.110
QLDA-P -13.31 -4.09 9.22 2.552 107.381 -3.609 4.610 0.217 -8.700 8.700 -0.184
QLDA-2P -16.51 -9.09 7.42 8.592 129.950 -3.533 3.710 0.270 -12.800 12.800 -0.782

MP2/6-31G
QL-P -13.12 -3.42 9.70 3.437 100.582 -2.128 4.850 0.206 -8.270 8.270 -0.131
QLD-P -12.95 -3.11 9.84 2.960 95.208 -2.700 4.920 0.203 -8.030 8.030 -0.105
QLDA-P -13.26 -4.19 9.07 2.942 129.511 -3.346 4.535 0.221 -8.725 8.725 -0.190
QLDA-2P -16.46 -9.11 7.35 8.204 132.006 -3.270 3.675 0.272 -12.785 12.785 -0.787

RHF/ 6-31G(d.p)
QL-P -13.22 -3.16 10.06 3.290 104.776 -1.600 5.030 0.199 -8.190 8.190 -0.118
QLD-P -13.04 -2.79 10.25 2.808 124.005 -2.040 5.125 0.195 -7.915 7.915 -0.089
QLDA-P -13.30 -3.63 9.67 2.794 116.677 -2.668 4.835 0.207 -8.465 8.465 -0.151
QLDA-2P -16.56 -8.30 8.26 8.576 101.379 -2.457 4.130 0.242 -12.430 12.430 -0.657

B3LYP/6-31G(d.p)
QL-P -11.14 -6.85 4.29 3.130 114.222 -1.082 2.145 0.466 -8.995 8.995 -0.465
QLD-P -10.93 -6.51 4.42 2.621 104.896 -1.553 2.210 0.452 -8.720 8.720 -0.389
QLDA-P -11.18 -7.20 3.98 2.984 120.565 -2.051 1.990 0.503 -9.190 9.190 -0.550
QLDA-2P -14.64 -11.96 2.68 7.332 115.924 -1.863 1.340 0.746 -13.300 13.300 -2.351

B3LYP/6-31G ++(d.p)
QL-P -11.28 -7.03 4.25 2.984 110.201 -2.720 2.125 0.471 -9.155 9.155 -0.507
QLD-P -11.07 -6.69 4.38 2.637 112.560 -2.928 2.190 0.457 -8.880 8.880 -0.429
QLDA-P -11.36 -7.43 3.93 2.953 130.329 -3.576 1.965 0.509 -9.395 9.395 -0.609
QLDA-2P -14.75 -12.12 2.63 7.703 105.154 -3.617 1.315 0.760 -13.435 13.435 -2.447

BP86/CEP-31G
QL-P -10.47 -7.65 2.82 2.870 93.413 -2.077 1.410 0.709 -9.060 9.060 -0.730
QLD-P 10.25 -7.30 -17.55 2.579 99.624 -2.184 -8.775 -0.114 1.475 -1.475 -0.483
QLDA-P -10.54 -8.00 2.54 2.987 112.121 -1.984 1.270 0.787 -9.270 9.270 -0.894
QLDA-2P -14.00 -12.62 1.38 7.499 141.924 -1.739 0.690 1.449 -13.310 13.310 -4.572

a
µ is the dipole moment, MV is the Molecular Volume, TNC is the sum of the total negative charge,  is the global hardness,  is the global softness,  is the chemical potential,  is the
electronegativity and ∆N is the fraction of the electrons that the inhibitor could transferred to the metal. The letter P in the name denote the protonated species.
Int. J. Electrochem. Sci., Vol. 7, 2012 5666

Table 7. The calculated condensed Fukui functions for electrophilic attack (f ) for the protonated species.
Method and molecule Atom of interest
C1 C2 N3 C5 C6 C7 C8 C9 C10

MP2/3-21G
QL 1.01 5.17 6.91 7.25 4.15 28.29 15.29 4.33 27.49
QLD 5.68 6.72 6.69 3.95 28.47 15.69 4.01 27.56
QLDA 4.96 6.97 7.34 4.66 28.26 15.05 4.51 27.11

MP2/6-31G
QL 1.41 5.24 6.96 8.15 4.07 27.84 14.01 4.52 27.76
QLD 1.41 5.68 6.85 7.64 3.85 27.96 14.32 4.25 27.95
QLDA 1.13 5.29 7.07 7.94 4.63 27.91 14.37 4.38 27.18

RHF/ 6-31G(d.p)
QL 2.23 4.15 6.46 8.95 3.77 27.12 12.38 6.32 28.15
QLD 3.28 3.70 5.91 9.62 3.49 27.00 10.70 7.18 28.63
QLDA 1.82 3.95 6.71 8.86 4.22 27.07 12.88 6.33 27.65

B3LYP/6-31G(d.p)
QL 2.46 4.58 6.72 8.67 4.22 28.28 11.60 5.64 27.32
QLD 2.56 4.61 6.65 8.53 4.12 28.36 11.44 5.66 27.46
QLDA 2.36 4.39 6.74 8.81 4.54 28.09 11.54 5.79 27.08

B3LYP/6-31G ++(d.p)
QL 2.41 4.57 6.61 8.86 4.27 28.38 11.51 5.58 27.44
QLD 2.52 4.60 6.54 8.74 4.15 28.44 11.37 5.59 27.60
QLDA 2.33 4.35 6.63 8.95 4.58 28.25 11.43 5.73 27.22

BP86/CEP-31G
QL 2.65 4.87 6.33 8.76 4.12 28.54 11.37 5.49 27.29
QLD 2.61 4.91 6.35 8.51 4.05 28.62 11.45 5.39 27.40
QLDA 2.67 4.61 6.31 8.99 4.39 28.28 11.13 5.73 27.12
Int. J. Electrochem. Sci., Vol. 7, 2012 5667

Table 8. The calculated condensed Fukui functions for nucleophilic attack (f +) for the protonated species.
Method and Atom of interest
molecule
C1 C2 N3 C4 C5 C6 C7 C8 C9 C10

MP2/3-21G
QL 5.23 13.75 23.02 2.07 31.55 8.09 2.30 9.13 4.16
QLD 4.73 12.77 22.34 3.35 31.10 8.51 1.97 9.26 4.38
QLDA 3.18 3.03 15.43 24.11 22.90 4.85 3.74 5.14 3.73

MP2/6-31G
QL 5.50 12.33 23.91 1.90 31.61 8.49 2.29 9.22 4.09
QLD 5.27 11.25 22.22 3.14 31.50 8.90 1.83 9.52 4.10
QLDA 3.26 3.52 13.76 24.11 22.40 4.90 3.80 5.17 3.55

RHF/ 6-31G(d.p)
QL 1.11 5.72 11.80 22.49 3.02 31.21 8.08 2.47 9.43 4.19
QLD 5.00 10.89 21.93 4.55 30.88 8.53 2.07 9.49 4.42
QLDA 2.85 4.34 13.00 23.75 25.41 5.81 3.67 6.50 3.82

B3LYP/6-31G(d.p)
QL 1.74 5.44 15.11 23.01 2.38 28.91 7.33 3.10 8.43 4.06
QLD 1.20 4.94 14.10 22.02 3.55 28.49 7.79 2.74 8.51 4.25
QLDA 3.44 4.25 15.72 22.27 21.83 4.73 4.21 5.74 3.80

B3LYP/6-31G
++(d.p)
QL 1.85 5.51 13.86 23.81 2.77 29.04 7.04 3.17 8.43 4.01
QLD 1.15 5.18 13.25 22.30 3.59 29.16 7.51 2.79 8.55 4.10
QLDA 3.58 4.16 14.95 22.76 21.86 4.35 4.35 5.59 3.73

BP86/CEP-31G
QL 2.06 5.39 14.98 23.33 2.39 28.68 6.96 3.33 8.26 4.00
QLD 1.40 5.01 13.97 21.90 3.67 28.42 7.55 2.89 8.49 4.16
QLDA 3.80 4.26 15.60 22.13 20.96 4.20 4.50 5.56 3.75
Int. J. Electrochem. Sci., Vol. 7, 2012 5668

Table 9. The calculated Mulliken atomic charges (e) and the bond distances (Ǻ) for non-protonated compounds in water solution.
Method Net atomic charge Bond Distance
and
Molecule N3 O12 O13 Fe18 C1-C2 C2-N3 N3-C4 C4-C5 C5-C6 C1-C6 C1-C7 C7-C8 C8-C9 C9-C10 C2-C10 C4-C11 C11-O12 C11-13 N3-Fe18

MP2/3-21G
QL -0742 - - - 1.437 1.398 1.348 1.428 1.386 1.432 1.433 1.387 1.431 1.387 1.429 - - - -
QLD -0.769 - - - 1.435 1.399 1.347 1.434 1.383 1.433 1.431 1.388 1.430 1.388 1.429 1.522 - - -
QLDA -0.728 -0.664 -0.723 - 1.439 1.395 1.345 1.425 1.384 1.431 1.431 1.388 1.431 1.387 1.429 1.504 1.244 1.371 -

MP2/6-31G
QL -0.654 - - - 1.442 1.401 1.353 1.431 1.393 1.435 1.437 1.395 1.435 1.394 1.432 - - - -
QLD -0.689 - - - 1.440 1.401 1.354 1.438 1.390 1.436 1.436 1.395 1.434 1.395 1.432 1.517 - - -
QLDA -0.617 -0.647 -0.764 - 1.444 1.395 1.355 1.432 1.392 1.433 1.435 1.395 1.436 1.394 1.433 1.500 1.259 1.378 -

RHF/ 6-31G(d.p)
QL -0.639 - - - 1.407 1.360 1.296 1.417 1.357 1.419 1.420 1.360 1.418 1.360 1.419 - - - -
QLD -0.674 - - - 1.404 1.363 1.296 1.427 1.353 1.421 1.417 1.361 1.416 1.362 1.417 1.506 - - -
QLDA -0.633 -0.614 -0.614 - 1.408 1.353 1.295 1.415 1.358 1.415 1.421 1.359 1.420 1.358 1.421 1.505 1.197 1.309 -

B3LYP/6-31G(d.p)
QL -0.556 - - - 1.433 1.370 1.322 1.418 1.375 1.419 1.421 1.378 1.418 1.378 1.421 - - - -
QLD -0.597 - - - 1.430 1.370 1.323 1.427 1.372 1.420 1.419 1.379 1.417 1.379 1.420 1.508 - - -
QLDA -0.604 -0.523 -0.519 - 1.434 1.363 1.323 1.419 1.374 1.417 1.420 1.377 1.419 1.377 1.422 1.503 1.221 1.337 -

B3LYP/6-31G ++(d.p)
QL -0.266 - - - 1.433 1.371 1.323 1.419 1.377 1.420 1.422 1.380 1.420 1.380 1.422 - - - -
QLD -0.273 - - - 1.431 1.372 1.324 1.428 1.373 1.421 1.421 1.381 1.419 1.381 1.421 1.508 - - -
QLDA -0.265 -0.565 -0.494 - 1.435 1.363 1.324 1.420 1.376 1.418 1.421 1.379 1.421 1.379 1.423 1.504 1.225 1.336 -

BP86/CEP-31G
QL 0.559 - - - 1.462 1.386 1.343 1.444 1.406 1.442 1.446 1.409 1.444 1.410 1.445 - - - -
QLD 0.648 - - - 1.459 1.386 1.344 1.452 1.402 1.443 1.445 1.410 1.443 1.411 1.444 1.527 - - -
QLDA 0.690 -0.101 -0.183 - 1.462 1.378 1.343 1.444 1.404 1.441 1.444 1.409 1.445 1.408 1.446 1.524 1.245 1.360 -

B3LYP/6-31G ++(d.p) (Fe-Complex)

QL -0.181 - - - 1.435 1414 1.382 1.391 1.393 1.421 1.425 1.384 1.412 1.389 1.409 - - - 1.798
QLD -0.693 - - - 1.428 1.408 1.362 1.409 1.376 1.418 1.420 1.379 1.412 1.381 1.414 1.506 - - 1.814
QLDA -0.241 -0.733 -0.624 - 1.427 1.415 1.429 1.421 1.365 1.449 1.410 1.395 1.401 1.396 1.405 1.403 1.248 1.419 1.804
Int. J. Electrochem. Sci., Vol. 7, 2012 5669

Table 10. The calculated Mulliken atomic charges for the heteroatom and selected the bond distances (Å) for protonated compounds in water
solution.
Method Net atomic charge Bond Distance
and
Molecule N3 O12 O13 Fe18 C1-C2 C2-N3 N3-C4 C4-C5 C5-C6 C1-C6 C1-C7 C7-C8 C8-C9 C9-C10 C2-C10 C4-C11 C11-O12 C11-13

MP2/3-21G
QL -0954 - - - 1.434 1.388 1.349 1.409 1.390 1.425 1.433 1.384 1.432 1.385 1.424 - - -
QLD -0.995 - - - 1.430 1.390 1.350 1.416 1.386 1.426 1.432 1.385 1.431 1.386 1.423 1.515 - -
QLDA -0.993 -0.576 -0.689 - 1.440 1.383 1.348 1.406 1.388 1.426 1.431 1.385 1.432 1.384 1.424 1.499 1.235 1.376

MP2/6-31G
QL -0.983 - - - 1.439 1.391 1.352 1.414 1.396 1.429 1.437 1.392 1.436 1.392 1.428 - - -
QLD -1.037 - - - 1.435 1.395 1.355 1.423 1.393 1.430 1.436 1.392 1.435 1.393 1.427 1.510 - -
QLDA -1.046 -0.549 -0.768 - 1.444 1.385 1.358 1.416 1.396 1.429 1.435 1.392 1.437 1.392 1.429 1.496 1.249 1.381

RHF/ 6-31G(d.p)
QL -0.717 - - - 1.402 1.366 1.315 1.390 1.368 1.414 1.418 1.358 1.416 1.362 1.407 - - -
QLD -0.772 - - - 1.397 1.373 1.316 1.405 1.360 1.420 1.415 1.362 1.412 1.365 1.404 1.497 - -
QLDA -0.771 -0.533 -0.618 - 1.407 1.357 1.321 1.381 1.377 1.404 1.423 1.355 1.421 1.359 1.410 1.507 1.183 1.309

B3LYP/6-31G(d.p)
QL -0.570 - - - 1.427 1.375 1.335 1.396 1.383 1.414 1.420 1.376 1.417 1.379 1.408 - - -
QLD -0.627 - - - 1.422 1.379 1.339 1.408 1.377 1.418 1.418 1.378 1.415 1.381 1.407 1.495 - -
QLDA -0.642 -0.448 -0.503 - 1.431 1.369 1.340 1.395 1.385 1.412 1.420 1.375 1.419 1.378 1.410 1.501 1.209 1.338

B3LYP/6-31G ++(d.p)
QL -0.093 - - - 1.427 1.376 1.336 1.397 1.384 1.415 1.421 1.378 1.418 1.381 1.409 - - -
QLD -0.088 - - - 1.422 1.380 1.339 1.410 1.378 1.419 1.419 1.379 1.416 1.382 1.408 1.495 - -
QLDA -0.104 -0.477 -0.475 - 1.432 1.369 1.342 1.395 1.386 1.412 1.421 1.376 1.421 1.379 1.411 1.501 1.211 1.338

BP86/CEP-31G
QL 0.454 - - - 1.454 1.390 1.352 1.425 1.411 1.439 1.444 1.408 1.443 1.411 1.432 - - -
QLD -0.454 - - - 1.449 1.394 1.357 1.435 1.405 1.440 1.442 1.408 1.440 1.411 1.431 1.513 - -
QLDA 0.535 -0.055 -0.223 - 1.458 1.384 1.359 1.422 1.411 1.436 1.443 1.406 1.444 1.408 1.433 1.520 1.232 1.361
 Int. J. Electrochem. Sci., Vol. 7, 2012 5670

Table 11. The calculated quantum chemical parametersa for non-protonated compounds in water solution.
Method and EHOMO (eV) ELUMO (eV) ∆E (eV) dipole molecular sum of the global Softness chemical Electronegativity fraction of
molecule moment volume total hardness  (eV-1) potential  (eV) electrons
µ (D) MV negative  (eV) Pi (eV) transferred
(cm3/mol) charge ∆N (e)
TNC (e)
MP2/3-21G
QL -9.47 0.67 10.14 5.170 90.362 -2.471 5.070 0.197 -4.400 4.400 0.256
QLD -9.48 0.67 10.15 3.872 103.717 -3.131 5.075 0.197 -4.405 4.405 0.256
QLDA -9.60 -0.14 9.46 2.876 95.310 -3.705 4.730 0.211 -4.870 4.870 0.255

MP2/6-31G(d,p)
QL -9.27 0.69 9.96 5.092 100.433 -2.177 4.980 0.201 -4.290 4.290 0.272
QLD -9.28 0.75 10.03 3.855 113.590 -2.737 5.015 0.199 -4.265 4.265 0.273
QLDA -9.42 -0.29 9.13 3.438 126.618 -3.432 4.565 0.219 -4.855 4.855 0.235

RHF/ 6-31G(d.p)
QL -9.33 0.99 10.32 5.108 119.635 -1.639 5.160 0.194 -4.170 4.170 0.274
QLD -9.33 1.11 10.44 3.935 129.998 -2.068 5.220 0.192 -4.110 4.110 0.277
QLDA -9.46 0.31 9.77 3.104 134.173 -2.746 5.885 0.205 -4.575 4.575 0.248

B3LYP/6-31G(d.p)
QL -7.20 -2.74 4.46 4.651 93.002 -1.097 2.230 0.448 -4.970 4.970 0.455
QLD -7.36 -2.82 4.51 6.487 123.068 -1.562 2.270 0.441 -5.090 5.490 0.421
QLDA -7.33 -3.30 4.03 3.401 131.698 -2.098 2.015 0.496 -5.315 5.315 0.418

B3LYP/6-31G
++(d.p)
QL -7.35 -2.93 4.42 4.776 79.355 -2.783 2.210 0.452 -5.140 5.140 0.421
QLD -7.33 -2.82 4.51 3.748 114.015 -3.097 2.255 0.443 -5.075 5.075 0.427
QLDA -7.50 -3.53 3.97 3.672 122.182 -3.717 1.985 0.504 -5.515 5.515 0.374

BP86/CEP-31G
QL -6.57 -3.60 2.97 4.642 104.412 -2.298 1.485 0.673 -5.085 5.085 0.645
QLD -6.54 -3.48 3.06 3.681 140.928 -2.246 1.530 0.654 -5.010 5.010 0.650
QLDA -6.71 -4.14 2.57 3.774 125.006 -2.272 1.285 0.778 -5.425 5.425 0.613
a
µ is the dipole moment, MV is the Molecular Volume, TNC is the sum of the total negative charge,  is the global hardness,  is the global softness,  is the chemical potential,  is the
electronegativity and ∆N is the fraction of the electrons transferred.
 Int. J. Electrochem. Sci., Vol. 7, 2012 5671

Table 12. The calculated quantum chemical parametersa for protonated compounds in water solution.
Method and EHOMO ELUMO (eV) ∆E (eV) dipole Molecular sum of the global Softness chemical Electronegativity fraction of
molecule (eV) moment volume total hardness  (eV-1) potential  (eV) electrons
µ (D) MV negative  (eV) Pi (eV) transferred
(cm3/mol) charge (e) ∆N (e)
MP2/3-21G
QL -9.47 0.67 10.14 5.170 90.362 -2.471 5.070 0.197 -4.400 4.400 0.256
QLD -9.48 0.67 10.15 3.872 103.717 -3.131 5.075 0.197 -4.405 4.405 0.256
QLDA -9.60 -0.14 9.46 2.876 95.310 -3.705 4.730 0.211 -4.870 4.870 0.255

MP2/6-31G(d,p)
QL -9.27 0.69 9.96 5.092 100.433 -2.177 4.980 0.201 -4.290 4.290 0.272
QLD -9.28 0.75 10.03 3.855 113.590 -2.737 5.015 0.199 -4.265 4.265 0.273
QLDA -9.42 -0.29 9.13 3.438 126.618 -3.432 4.565 0.219 -4.855 4.855 0.235

RHF/ 6-31G(d.p)
QL -9.33 0.99 10.32 5.108 119.635 -1.639 5.160 0.194 -4.170 4.170 0.274
QLD -9.33 1.11 10.44 3.935 129.998 -2.068 5.220 0.192 -4.110 4.110 0.277
QLDA -9.46 0.31 9.77 3.104 134.173 -2.746 5.885 0.205 -4.575 4.575 0.248

B3LYP/6-31G(d.p)
QL -7.20 -2.74 4.46 4.651 93.002 -1.097 2.230 0.448 -4.970 4.970 0.455
QLD -7.36 -2.82 4.51 6.487 123.068 -1.562 2.270 0.441 -5.090 5.490 0.421
QLDA -7.33 -3.30 4.03 3.401 131.698 -2.098 2.015 0.496 -5.315 5.315 0.418

B3LYP/6-31G
++(d.p)
QL -7.35 -2.93 4.42 4.776 79.355 -2.783 2.210 0.452 -5.140 5.140 0.421
QLD -7.33 -2.82 4.51 3.748 114.015 -3.097 2.255 0.443 -5.075 5.075 0.427
QLDA -7.50 -3.53 3.97 3.672 122.182 -3.717 1.985 0.504 -5.515 5.515 0.374

BP86/CEP-31G
QL -6.57 -3.60 2.97 4.642 104.412 -2.298 1.485 0.673 -5.085 5.085 0.645
QLD -6.54 -3.48 3.06 3.681 140.928 -2.246 1.530 0.654 -5.010 5.010 0.650
QLDA -6.71 -4.14 2.57 3.774 125.006 -2.272 1.285 0.778 -5.425 5.425 0.613
a
µ is the dipole moment, MV is the Molecular Volume, TNC is the sum of the total negative charge,  is the global hardness,  is the global softness,  is the chemical potential,  is the
electronegativity and ∆N is the fraction of the electrons transferred
Int. J. Electrochem. Sci., Vol. 7, 2012 5672

Table 13. The calculated condensed Fukui functions for electrophilic attack (f ) for the non-protonated species in water solution.
method and molecule Atom of interest
C2 N3 C4 C5 C6 C7 C8 C9 C10
MP2/3-21G
QL 12.10 3.02 8.77 10.99 22.72 10.16 7.90 23.41
QLD 1.16 12.80 4.34 6.26 10.19 22.24 12.51 5.88 23.51
QLDA 10.42 2.13 10.78 10.91 23.37 8.47 9.38 23.21

MP2/6-31G
QL 11.91 2.48 8.85 10.43 23.10 10.31 7.93 23.77
QLD 2.16 12.61 3.78 6.17 9.61 22.60 12.88 5.75 23.89
QLDA 10.14 1.80 10.77 10.44 23.78 8.63 9.38 23.45

RHF/ 6-31G(d.p)
QL 1.52 10.06 2.56 8.23 9.56 23.49 11.40 8.32 24.20
QLD 3.88 10.59 4.65 4.42 8.33 22.67 15.62 4.84 23.79
QLDA 8.82 1.75 10.16 9.62 23.90 9.56 10.02 23.91

B3LYP/6-31G(d.p)
QL 1.29 10.49 2.65 8.45 10.15 23.86 9.85 8.33 24.07
QLD 2.19 11.35 3.86 6.04 9.56 23.14 11.91 6.45 24.25
QLDA 1.19 9.22 2.15 9.53 9.72 24.35 9.09 8.99 24.13

B3LYP/6-31G ++(d.p)
QL 1.26 10.30 2.29 8.64 10.01 24.07 9.83 8.29 24.42
QLD 2.25 11.12 3.29 6.45 9.39 23.40 11.87 6.46 24.51
QLDA 1.17 8.88 1.68 9.95 9.60 24.58 8.94 9.08 24.38

BP86/CEP-31G
QL 1.33 9.97 2.39 8.74 9.63 24.31 9.56 8.47 24.56
QLD 2.07 10.88 3.49 6.51 9.10 23.58 11.44 6.75 24.81
QLDA 1.24 8.58 1.85 10.04 9.06 24.78 8.70 9.18 24.61
Int. J. Electrochem. Sci., Vol. 7, 2012 5673

Table 14. The calculated condensed Fukui functions for nucleophilic attack (f +) for the non-protonated species in water solution.

Method and Atom of interest

molecule
N3 C4 C5 C6 C7 C8 C9 C10 C11 O12 O13
MP2/3-21G
QL 15.92 10.39 8.03 22.94 14.56 5.34 8.70 13.73
QLD 14.48 9.18 9.46 22.59 15.21 4.70 9.47 13.91
QLDA 20.37 16.00 14.97 7.02 8.99 2.06 9.97 8.82 6.41 1.52

MP2/6-31G
QL 15.87 11.89 7.58 23.85 13.81 5.01 8.51 12.70
QLD 14.28 10.33 9.25 23.62 14.54 4.27 9.46 12.87
QLDA 20.12 16.30 13.13 5.39 8.54 1.54 8.43 13.06 7.21 1.60

RHF/ 6-31G(d.p)
QL 13.65 11.52 8.83 22.69 13.84 5.49 9.07 13.04
QLD 12.01 9.70 10.78 22.31 14.57 4.56 10.20 13.31
QLDA 17.58 17.92 15.44 7.69 9.39 2.48 9.55 8.83 4.75 1.12

B3LYP/6-
31G(d.p)
QL 16.37 12.23 7.56 22.82 13.03 5.81 7.77 12.47
QLD 14.88 10.75 9.22 22.34 13.78 5.23 8.44 12.74
QLDA 19.28 15.73 14.26 6.11 8.48 2.43 9.29 9.66 7.61 2.34

B3LYP/6-31G
++(d.p)
QL 14.96 13.36 8.89 22.15 12.43 5.99 7.91 12.60
QLD 13.85 11.01 10.02 22.43 13.40 5.29 8.88 12.67
QLDA 18.35 16.30 13.83 5.11 8.66 2.15 9.14 11.66 7.84 2.47

BP86/CEP-31G
QL 16.06 12.51 7.56 23.08 12.75 5.82 7.68 12.46
QLD 14.40 10.54 9.64 22.57 13.74 5.02 8.59 12.73
QLDA 18.88 15.35 13.68 5.34 8.37 2.36 9.22 10.45 8.49 2.83
Int. J. Electrochem. Sci., Vol. 7, 2012 5674

Table 15. The calculated condensed Fukui functions for electrophilic attack (f ) for the protonated species in water solution.
Method and molecule Atom of interest
C1 C2 N3 C5 C6 C7 C8 C9 C10

MP2/3-21G(d,p)
QL 1.20 3.20 7.95 9.50 5.12 26.51 12.07 6.54 27.75
QLD 1.18 3.80 7.91 8.71 4.79 26.74 12.85 5.95 27.96
QLDA 1.17 3.65 7.73 9.08 5.14 26.90 12.74 6.04 27.47

MP2/6-31G
QL 1.43 3.50 7.72 9.59 5.01 26.48 12.07 6.51 27.67
QLD 1.64 3.76 7.44 9.37 4.61 26.72 12.00 6.44 27.98
QLDA 1.08 4.19 7.54 8.80 5.04 27.01 13.24 5.75 27.28

RHF/ 6-31G(d.p)
QL 2.17 2.85 6.89 10.14 4.73 26.01 10.90 8.20 27.67
QLD 3.95 2.44 6.22 11.03 4.29 25.88 9.11 9.25 27.92
QLDA 1.55 3.27 7.05 9.29 4.72 26.35 12.35 7.52 27.40

B3LYP/6-31G(d.p)
QL 2.01 3.52 7.37 9.23 5.24 27.29 10.77 7.01 27.00
QLD 16.46 12.94 22.21 1.16 1.67 9.19 15.99
QLDA 2.07 3.76 7.07 9.09 5.00 27.47 10.99 6.89 26.90

B3LYP/6-31G ++(d.p)
QL 1.95 3.41 7.28 9.47 5.34 27.29 10.70 7.06 27.08
QLD 2.16 3.53 7.12 9.47 5.04 27.43 10.47 7.13 27.21
QLDA 2.02 3.70 6.95 9.27 5.06 27.54 10.96 6.92 27.06

BP86/CEP-31G
QL 2.14 3.70 7.02 9.34 5.11 27.54 10.52 6.97 27.04
QLD 2.20 3.83 6.97 9.17 4.88 27.67 10.54 6.87 27.16
QLDA 2.33 3.93 6.63 9.30 4.78 27.67 10.58 6.91 27.08
Int. J. Electrochem. Sci., Vol. 7, 2012 5675

Table 16. The calculated condensed Fukui functions for nucleophilic attack (f +) for the protonated species in water solution.

Method and Atom of interest

molecule
C1 C2 N3 C4 C5 C6 C7 C8 C9 C10

MP2/3-21G
QL 3.73 13.37 20.62 3.52 30.18 10.01 2.50 9.53 6.27
QLD 3.84 12.46 19.52 3.89 30.12 9.92 2.16 9.55 5.86
QLDA 2.69 2.29 15.28 23.24 22.77 5.76 4.06 5.02 4.81

MP2/6-31G
QL 4.34 12.40 3.20 30.39 9.84 2.42 9.38 5.82
QLD 4.31 11.56 21.05 3.93 30.24 9.92 2.03 9.53 5.61
QLDA 3.23 2.77 14.16 23.39 20.92 4.95 4.10 4.49 4.14

RHF/ 6-31G(d.p)
QL 4.40 11.84 21.21 4.32 29.78 9.27 2.72 9.37 5.94
QLD 4.03 11.07 20.90 5.32 29.42 9.51 2.33 9.42 5.96
QLDA 2.78 3.50 13.43 23.36 24.21 6.05 4.10 5.42 4.61

B3LYP/6-
31G(d.p)
QL 1.22 4.36 15.22 21.59 3.33 28.15 8.43 3.37 8.26 5.60
QLD 2.05 16.26 4.32 4.58 12.94 17.96 13.61 3.70 21.90
QLDA 3.42 3.58 16.13 21.56 20.66 4.82 4.59 5.09 4.48

B3LYP/6-31G
++(d.p)
QL 1.36 4.20 13.83 22.30 4.06 28.06 8.18 3.50 8.31 5.71
QLD 4.12 13.47 21.20 4.22 28.28 8.41 3.15 8.40 5.58
QLDA 3.64 3.27 15.30 21.80 20.41 4.33 4.81 4.84 4.46

BP86/CEP-31G
QL 1.46 4.24 15.10 21.69 3.43 27.97 8.22 3.57 8.11 5.63
QLD 1.05 4.07 14.22 20.75 4.33 27.56 8.56 3.17 8.29 5.63
QLDA 3.82 3.56 16.01 21.19 19.57 4.23 4.88 4.85 4.45
Int. J. Electrochem. Sci., Vol. 7, 2012 5676

Table 17. The calculated quantum chemical parameters for the Fe- inhibitor complexes (DFT/B3LYP/6-31G ++(d, p) results in vacuo).

Quantum parameters Molecules

QL QLD QLDA

Interaction energy (eV) -1.653 -1.529 -2.211

EHOMO (eV) -4.03 -3.85 -4.42
ELUMO (eV) -2.21 -2.06 -2.29
∆E (eV) 1.82 1.79 2.13
dipole moment, µ (D) 4.530 4.287 1.911
molecular volume ,MV (cm3/mol) 95.4 138.7 167.9
sum of the total negative charge, TNC (e) -3.130 -4.227 -3.744
global hardness,  (eV) 0.910 0.895 1.065
global softness,  (eV-1) 1.099 1.117 0.939
chemical potential, Pi (eV) -3.120 -2.955 -3.355
electronegativity,  (eV) 3.120 2.955 3.355
fraction of electrons transferred, ∆N (e) 2.132 2.260 1.711

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