Journal of Molecular Liquids 279 (2019) 342–350

Contents lists available at ScienceDirect

Journal of Molecular Liquids

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

Understanding the corrosion inhibition of mild steel by selected green

compounds using chemical quantum based assessments and molecular
dynamics simulations
Kazeem O. Sulaiman a,⁎, Abdulmujeeb T. Onawole b, Omar Faye c, Damola T. Shuaib d
a
Department of Chemistry, University of Saskatchewan, 110 Science Place, Saskatoon, Saskatchewan S7N 5C9, Canada
b
Department of Chemistry, King Fahd University of Petroleum & Minerals (KFUPM), Dhahran 31261, Saudi Arabia
c
Department of Mechanical Engineering, College of Engineering, University of Saskatchewan, 57 Campus Drive, Saskatoon, Saskatchewan S7N 5A9, Canada
d
Department of Chemistry, Illinois Institute of Technology, Chicago, IL 60616, USA

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

Article history: Both quantum chemical calculations and molecular dynamics simulations enabled better understanding of mild
Received 2 September 2018 steel corrosion inhibitions by citrulline (CE), quercetin (QN), and bonducellin (BN) as green compounds, at mo-
Received in revised form 27 December 2018 lecular level. The theoretical study gave insights to the active sites, chemical reactivity and possible interaction
Accepted 25 January 2019
mechanism between the inhibitor compounds and mild steel surface. The compounds showed sufficient nucle-
Available online 28 January 2019
ophilicity in sulfuric acid medium to indicate their low propensity to accept electron from mild steel, to affirm
Keywords:
their corrosion inhibition effects. Based on the obtained theoretical parameters, these compounds could be
Adsorption ranked in the order of QN N BN N CE for their degrees of inhibition efficiencies. These compounds bound onto
Citrulline iron surface spontaneously with binding energies of 570.95 kcal/mol, 563.96 kcal/mol, and 539.23 kcal/mol for
Corrosion inhibition QN, BN, and CE respectively.
Density functional theory © 2019 Elsevier B.V. All rights reserved.
Green compounds
Mild steel
Molecular dynamics simulations

1. Introduction
The use of mild steel is foremost in several construction works, pos-
sibly due to its superb mechanical properties and comparatively
cheaper cost. Like other metals, however, its degradation, when in con-
tact with corrosion agents like acids, is a considerable issue for its exten-
sive use [1]. For instance, essential processes like pickling, descaling and
oil well acidizing employ acids such as hydrochloric (HCl) and sulfuric
(H2SO4) acid solutions, with the disadvantage of corroding metal com-
ponents [2]. National Association of Corrosion Engineers (NACE) report-
edly projected the global cost of corrosion to be US$2.5 trillion to
emphasis the cost management of the corrosion effects, not limited to
environmental damage and safety, in global society. Meanwhile, proper
implementation of corrosion control measures can save about $875 bil-
lion annually [1,3]. This can be well achieved with the use of effective
corrosion inhibitors. Thus, research attention is geared towards explor-
ing existing materials as well as developing new materials that are capa-
ble of inhibiting metal corrosion in presence of acid.
⁎ Corresponding author.
E-mail address: kosulaiman2008@yahoo.com (K.O. Sulaiman).
Over time, the use of protective film and other substances, that can
offer excellent protection to the mild steel or metal materials, has
been identified as panacea to metal corrosion problem [4], so much
that current research interests focus on making cheap and effective ma-
terials for corrosion inhibition, without underestimating the need to un-
derstand the inhibition process. Synergizing the knowledge about
corrosion inhibition process through both experimental and theoretical
studies has led to the development of efficient materials that inhibit
metal degradation via metal surface protection [4,5]. The known effec-
tive materials are both of synthetic and natural sources, and in the inter-
est of environmental safety, those with greater potential of being eco-
friendly are mostly preferred [6].
Organic heterocyclic compounds containing heteroatoms such as
oxygen (O), nitrogen (N), sulfur (S) and phosphorus (P), constitute
vast number of effective inhibitors. The heteroatoms serve as active
sites for the adsorption onto the metal surface and the adsorption can
be through physisorption and/or chemisorption process [7]. Inhibitors
can possibly adsorb so well to form protective layers on metal surfaces
and thus enable better resistance to surface degradation in the presence
of acid solution. Meanwhile, many of these organic inhibitors are exor-
bitant and less environmentally friendly, and these major demerits fa-
cilitate the exploration and development of green inhibitors that are

https://doi.org/10.1016/j.molliq.2019.01.136
0167-7322/© 2019 Elsevier B.V. All rights reserved.
 K.O. Sulaiman et al. / Journal of Molecular Liquids 279 (2019) 342–350
eco-friendly to enable environmental sustainability [8,9]. In contrast to
synthetic compounds, natural products, especially plant extracts are
the most common sources of green corrosion inhibitors and their effec-
tiveness in corrosion prevention is well reported in the literature
[10–14].
Although natural products are commonly used as green inhibi-
tors, yet understanding their corrosion inhibition mechanism is not
well documented. Perhaps, this is partly due to the fact that there
are different chemical compounds in plant extracts, such that identi-
fying active compound(s), with significant contribution(s) to the in-
hibitory property, can be challenging [9,15]. However, in few cases,
the major active compounds are known and that can facilitate their
specific corrosion inhibition studies, both experimentally and theo-
retically. Typical examples are watermelon (Citrullus lanatus),
apple (Malus domestica), bonduc (Caesalpinia bonducella) leaf ex-
tracts that are very rich sources of citrulline (CE), quercetin (QN),
and bonducellin (BN) respectively, as active agents against corrosion
of mild steel in acidic solution [16,17]. It is noteworthy that these
identified active agents typically have more than a source. They
may be found at different concentrations in different parts of the
same plant, or in different plant entirely [16,17].
Many parts of the watermelon contain CE as an active agent that
is responsible for their corrosion inhibition performance [17,18].
Specifically, the watermelon rind extract (WRE) was experimentally
found to have significant inhibitory effect against acid stimulated
corrosion of mild steel and CE was subsequently identified as the
major active inhibitor constituent of the WRE. The CE accounts for
about 51% of the total 90.2% inhibition efficiency of WRE [17]. On
its own, CE has been reported to be a mixed-type corrosion inhibitor
with about 46% inhibition efficiency, which decreases with increase
in temperature of the medium. However, the adsorption process of
the CE was only assumed to be physisorption, approximately
modeled by Temkin adsorption isotherm [17], and this assumption
gives a chance for more insightful molecular understanding of such
adsorption process on mild steel surface. Similarly, QN and BN
were also experimentally accessed to be a mixed-type green inhibi-
tors with inhibition efficiencies that increased in proportion to in-
crease in their concentration and decreased with increase in
solution temperature [19,20]. It was earlier reported that bonduc
and apple leaf extracts, containing BN and QN respectively as active
compounds, showed corrosion inhibition of mild steel in 0.5 M sulfu-
ric acid by physical adsorption using electrochemical measurements
[19]. Similar inadequacy can be identified like in the case of CE, such
that understanding of corrosion inhibition of these active com-
pounds, CE, BN, and QN, at molecular level is a research gap that
needs to be bridged.
Computational modeling is a simulative, predictive, and powerful
tool that helps in the mechanistic study of corrosion inhibitors [21,22].
In fact, several reports in the literature have remarked density func-
tional theory (DFT) as a reliable theoretical tool to evaluate the interac-
tion between inhibitor and metal surface [23–25]. However, the snag of
a simulation is to utilize a method that efficiently replicates the reality
that occurs experimentally. Most computational calculations do not
properly imitate the acidic environment in which the corrosion process
occurs. Rather than using ordinary water like in common practice, our
previous work [26] established the proper mimicking of the acidic envi-
ronment, that is simulation of water with high ionic strength, to circum-
vent the complexity of the surrounding environment of an inhibitor in
actual experimental scenario. This present study attempted to bridge
the identified knowledge gap by presenting molecular level insights to
the corrosion inhibition of CE, BN and QN as selected green inhibitors
using chemical quantum approach and molecular dynamics simula-
tions, as well as a better simulation of corrosion environment. These re-
vealed hitherto unrecognized connections between structure and
properties, which are essential for the complete understanding of
these green corrosion inhibitors.
343
2. Computational details
2.1. Quantum chemical calculations and parameters definition
All quantum chemical calculations were performed using DFT with
hybrid function of Becke three-parameters Lee, Yang and Parr
(B3LYP), that is DFT-B3LYP, method with Gaussian 09 software [27].
The 6-311G++ (d,p) basis set was used owing to the fact that it pro-
vides accurate electronic properties and geometries for a large number
of organic compounds, besides giving comparable results to those from
plane-wave calculations [28]. The calculations were carried out in both
gas and acidic media, and the Density-based Solvation Model-Self-Con-
sistent Reaction Field (SMD-SCRF) was applied to generate sulfuric acid
as acidic medium. SMD is a universal solution model, which is applicable
for both charged and uncharged molecules [29]. It is more accurate in
the calculation of cavitation and dispersion-repulsion energies which
gives excellent results for free energies of solvation than the Polarizable
Continuum Model (PCM) [29–32]. The H2SO4 medium was absent
among the default solvent media in Gaussian 09, and its simulation
was done using the calculated solvent parameters of 100 and 2.19 for
both static and optical dielectric constants respectively [33,34]. The de-
tail of similar calculation for HCl was previously reported [26] but in this
case, 1.48 was found on MSDS (material safety data sheet) as the refrac-
tive index of H2SO4 [35]. The Fukui functions were calculated via the Fi-
nite Difference (FD) method using the UCA-FUKUI v 1.0 software [36]
and the output file from Gaussian 09, while LeadIT was used to deter-
mine the protonation site in each compound [37].
The structural geometry of each of the studied green compounds
was firstly optimized, followed by the vibrational frequency analysis,
prior to other quantum chemical calculations whose outputs were
used to estimate some useful derived parameters such as electron affin-
ity (EA), ionization potential (IP), global hardness (η), electronegativity
(χ), global electrophilicity index (ω), and the quantity of electron trans-
ferred to metal atom from inhibitor molecule (ΔN) using Eqs. (1)–(7)
below. The ΔN was calculated using Eq. (7), where ηFe equals zero and
ϕFe is the work function of iron surface [38–40]. The sum of the nega-
tively charged atoms in the Mulliken charges analysis gives the total
negative charge (TNC) [41] and the Eqs. (8)–(9) were used to calculate
the Fukui functions, where the P(N + 1), P(N) and P(N-1) represent the
charge values for cation, neutral and anion of the selected atoms respec-
tively [42].
EA ¼ −ELUMO ð1Þ
IP ¼ −EHOMO ð2Þ
η ¼ ðIP−EAÞ=2 ð3Þ
χ ¼ ðIP þ EAÞ=2 ð4Þ
ω ¼ μ 2 =2η ð5Þ
ρ ¼ 1=η ð6Þ
ΔN ¼ ½ϕFe −χinh =½2 ðηFe þ ηinh Þ ð7Þ
þ
f k ¼ PðN þ 1Þ−PðNÞ ð8Þ
−
f k ¼ PðNÞ−PðN−1Þ ð9Þ
2.2. Molecular dynamics simulation
The Forcite module implemented in Materials Studio software was
used to evaluate the nature of the interaction between the adsorbate
and the iron sorbent. Fe crystal was cleaved along (111), (110), and
(100) surfaces but Fe (110) surface was identified to have the most
344 K.O. Sulaiman et al. / Journal of Molecular Liquids 279 (2019) 342–350
stabilization compared to other Fe surfaces, and thus Fe (110) surface
was selected for further studies. Accordingly, Fe (110) surface reveals
more active sites for interaction with inhibitors [43], hence we
employed a supercell 8 × 8 × 1 of Fe (110) surface, with periodic bound-
aries conditions along the x and y directions, to study our systems. The
Fe (110) was fabricated with periodic slab surfaces that consist four
atomic layers and a vacuum slab with 21 Å thickness was made above
the Fe (110) plane. The calculations were carried out in the NVT canon-
ical ensemble at 300 K with a time step of 0.1 fs and a total simulation
period of 0.5 ps using an Anderson thermostat. The condensed-phase
optimized molecular potentials for atomistic simulation studies (COM-
PASS) force field was used for geometry optimization of structures
[44]. The COMPASS force field is an ab initio force field that provides cor-
rect predictions of gas phase properties like conformational, structural,
vibrational as well as the condensed phase properties such as cohesive
energies and interaction energies for a wide range of organic molecules,
inorganic molecules and metals [45–47]. The interaction and binding
energies of each molecule with the Fe surface were obtained using the
Eqs. (10) and (11) below:

The constituent heteroatoms serve as active adsorption sites for the
Einteraction ¼ Etotal – Esurface þ Emolecule


Ebinding ¼ − Etotal − Esurface þ Emolecule
where Etotal is the total energy of the molecules and the metal surface
system, Esurface is the energy of the metal surface without adsorption of
molecules, and Emolecule is the energy of the isolated inhibitor molecule.
3. Results and discussion
The molecular structures of the selected green compounds (CE, QN,
and BN) are presented in Fig. 1 to clearly show the composition and
numbering of atoms in the compounds. CE contains amide, amine and
carboxylic functional groups that afford oxygen (O) and nitrogen
(N) as heteroatoms while each of QN and BN has O as only heteroatom.
The Infra-Red (IR) spectra of the compounds were obtained and com-
pared with those obtained experimentally. These IR spectra are pre-
sented in Fig. 2 and it turns out that the theoretically calculated IR
bands for all the three inhibitors are in good agreement with those re-
ported from the FTIR measurements [17,19,48]. The CE shows IR
Fig. 1. (a) Chemical structures and (b) DFT optimized structures in H2SO4 medium, of CE, QN, and BN, using B3LYP/6311G++(d,p) level of theory.
bands for C\\N stretching at 800 cm−1, H\\C\\H bending at
1400 cm−1, C_O (carboxylic acid) stretching at 1635 cm−1, C_O (car-
bonyl) stretching at 1710 cm−1, CH\\ stretching at 2920 cm−1, and
\\NH and \\OH stretching at ca. 3430 cm−1 among others [18]. The
QN shows IR bands for C\\O aromatic ether, aromatic C_C, C_O,
C\\H stretching vibration, and O\\H band at 1103.17 cm−1 and
1202.2 cm−1, 1453.5 cm−1 and 1598.7 cm−1, 1687.8 cm−1,
2918.9 cm−1, and 33.23.2 cm−1 respectively. The BN shows IR bands
at 1042.1 cm−1, 1373.6 cm−1 and 1243.0 cm−1, 1449.1 cm−1 and
1650.2 cm−1, 1706.6 cm−1, 2848.9 cm−1, 2916.7 cm−1, and
3337.4 cm−1 for C\\O single bond of O-CH3, C\\O aromatic ether, aro-
matic C_C, C_O, C\\H sp2 stretching vibration, C\\H sp. stretching vi-
bration, and O\\H band [17]. Table 1 presents the structural parameters
in term of the bond lengths and bond angles for the optimized neutral
molecules calculated at the B3LYP/6-311G++ (d,p) level of theory, in
comparison with observed values experimentally [49–51]. The results
show significant level of agreement with some minor differences to sug-
gest that acidic environment does not significantly affect the spatial ar-
rangements of constituent atoms of these green inhibitor molecules.
ð10Þ compounds on the mild steel surface. Besides, the benzene rings in QN
and BN can also give π-electron in binding to electrophilic metal surface.
ð11Þ The molecular structures were optimized in DFT-B3LYP calculations in
both gas phase (Fig. S1) and simulated sulfuric acid medium (Fig. 1).
The structural geometry optimizations of the respective compounds re-
veal the spatial arrangement of constituent atoms. The observed non-
planar configurations can be related to the differences in the obtained
structural parameters for different molecular environment [52]. The vi-
brational frequency analyses of the optimized structures show the ab-
sence of imaginary frequency to indicate the true minimum in the
energy profiles.
The employed DFT-B3LYP method is suitable for rationalizing the
frontier molecular orbitals for the assessment of inhibitor-metal inter-
action [22]. The energy of highest occupied molecular orbital (EHOMO)
and that of lowest unoccupied molecular orbital (ELUMO) are directly ob-
tainable, alongside with the energy band gap (ΔELUMO-HOMO) from the
computational output. The qualitative descriptions of frontier molecular
orbitals, HOMO and LUMO, obtained in acidic medium are presented in
Fig. 3, which clearly show even distribution of molecular orbitals over
the entire molecules to suggest possible interactions, and thus almost
 K.O. Sulaiman et al. / Journal of Molecular Liquids 279 (2019) 342–350 345

Fig. 2. Theoretically calculated (a) and experimentally observed [48] (b) IR spectra of CE, QN, and BN.

parallel adsorption of molecules onto metal surface. Such evenly distrib-
uted molecular orbitals are not observed for molecules in gas phase, es-
pecially for CE (Fig. S1). Expectedly, differences due to molecular
environment reflect in all quantum chemical parameters (Tables 2 and
S1). Quantitatively, the EHOMO gives information about the electron do-
nating ability of the inhibitor while the ELUMO relates to its capability to
accept electrons. Higher EHOMO value depicts greater tendency of the in-
hibitor to donate electron to the metal with unoccupied molecular or-
bitals, while a lower ELUMO implies that the inhibitor would readily
accept electrons from the metal surface. By implication, a good inhibitor
will have both a high EHOMO value and a low ELUMO value, such that
smaller ΔELUMO-HOMO value will indicate better donating ability of the
molecular orbitals of the inhibitor to the metal surface molecular or-
bitals. Such frontier molecular orbital interactions results to high ad-
sorption of the inhibitor onto the metal surface, and thus reduces the
reaction of metal in acidic medium [53].
Zhang and Musgrave (2007) reported a convincing argument
against the accuracy of quantitative values for EHOMO and ΔELUMO-
HOMO without necessary correction factors, especially for small mole-
cules. Therein, depending on the DFT functional, equations were given
to obtain corrected values from uncorrected values, with experimental
validations [54]. With respect to the functional employed in this study,

Table 1
Experimentally observed and theoretically calculated (in gas phase and acidic medium) structural parameters of CE, QN, and BN calculated at B3LYP/6311G++(d,p) level of theory.

CE QN BN

Bond length Obs. Calculated Bond length Obs. Calculated Bond length Obs. Calculated

G A G A G A

N1-H2 0.899 1.009 1.012 O1-C2 1.365(7) 1.375 1.375 O1-C7 1.444 1.441 1.449
N1-H3 0.900 1.009 1.012 O1-C10 1.370(4) 1.359 1.359 O1-C8 1.364 1.357 1.354
C4-O5 1.257 1.220 1.234 O4-C3 1.267(7) 1.256 1.256 O2-C9 1.236 1.226 1.232
N6-H7 0.843 1.008 1.010 O18-C6 1.375(7) 1.340 1.34 C6-C9 1.464 1.475 1.474
C8-H9 0.970 1.096 1.091 O18-H28 0.948(5) 0.987 0.987 C5-C9 1.482 1.494 1.490
C8-H10 0.970 1.091 1.095 O19-C8 1.358(7) 1.361 1.361 O3-C14 1.351 1.363 1.358
C11-H12 0.969 1.097 1.097 O19-H29 0.914(5) 0.963 0.963 O3-H32 0.820 0.963 0.968
C11-H13 0.970 1.095 1.095 O20−C17 1.351(7) 1.355 1.355 O4-C20 1.364 1.359 1.355
C14-H15 0.970 1.094 1.095 O20-H30 0.906(3) 0.977 0.977 O4-C21 1.970 1.424 1.434
C14-H16 0.970 1.094 1.094 O21-C5 1.396(5) 1.357 1.357 – – – –
C17-N18 1.478 1.456 1.461 O21-H32 0.975(4) 0.967 0.967 – – – –
C17-C22 1.513 1.537 1.534 O22-C13 1.373(7) 1.377 1.377 – – – –
C17-H19 0.980 1.096 1.094 O22-H32 0.990(5) 0.962 0.962 – – – –
N18-H20 1.029 1.014 1.016 C2-C17 1.357(8) 1.369 1.369 – – – –
N18-H21 1.035 1.014 1.016 C2-C16 1.479(5) 1.462 1.462 – – – –
C22-O25 1.251 1.357 1.211 C17-C3 1.449(6) 1.449 1.449 – – – –
– – – – C3-C11 1.418(8) 1.434 1.434 – – – –

CE QN BN

Bond angle Obs. Calculated Bond angle Obs. Calc. Bond angle Obs. Calc.

G A G A G A

O5-C4-N1 120.03 122.13 121.68 C9-C10-C11 122.79(4) 122.186 122.3 C8-O1-C7 116.08 116.6 116.5
O23-C22-O25 125.12 122.15 122.24 C9-C10-O1 116.79(4) 117.433 117.4 C5-C9-C6 116.01 115.3 115.6
– – – – C11-C10-O1 120.42(5) 120.380 120.2 C6-C9-O2 121.69 122.1 121.8
– – – – C3-C11-C6 122.83(5) 119.263 122.3 C5-C9-O2 122.3 122.5 122.6
– – – – C3-C11-C10 120.17(4) 119.263 119.2 H32-O3-C14 109.46 109.8 109.9
– – – – C6-C11-C10 116.96(5) 118.667 118.4 C20-O4-C21 118.29 118.8 118.9
– – – – C2-C16-C14 121.34(5) 122.323 122.4 – – – –
– – – – C2-C16-C15 119.34(5) 119.399 119.2 – – – –
– – – – C14-C16-C15 119.30(4) 118.279 118.4 – – – –

Note: bond lengths are measured in Å while bond angles are measured in degrees. Atoms are numbered as shown in Fig. 1b. Also, ‘G’ represents gas phase while ‘A’ represents acidic
medium.
346 K.O. Sulaiman et al. / Journal of Molecular Liquids 279 (2019) 342–350

Fig. 3. Frontier molecular orbitals, HOMO and LUMO, for CE, QN, and BN in H2SO4 medium.

Eqs. (12) and (13) were used to obtain corrected values for both EHOMO
and ΔELUMO-HOMO. The uncorrected values are presented in Table S1
while corrected values for global chemical reactivity indices, and other
parameters derived thereof, are presented in Tables 2 and 3 respec-
tively.

action in forming good adsorption layers on metal surface in acidic me-
EHOMO;corrected ¼ 1:42 þ 1:20  EHOMO;uncorrected

enables the separation of their solute molecules. This notion is in line
ΔELUMO−HOMO;corrected ¼ −1:02 þ 0:93  ΔELUMO−HOMO;uncorrected
The electron-donating ability of the compounds follows the order of
CE b BN b QN with respect to the values of their EHOMO while the
electron-accepting ability follows the order of CE N BN ~ QN (Table 2).
While QN has almost the same value for energy gaps in gas phase and
in sulfuric acid medium, BN shows lower values for the energy gaps in
acidic medium than in gas phase to indicate more reactivity, and thus
increase in adsorption of molecule onto metal surface, in acidic medium.
In contrast, CE shows greater values for energy gap in acid medium than
in gas phase, to suggest its probably lesser reactivity in acidic medium.
The energy gap of 2.323 eV, 2.434 eV, and 4.908 eV are obtained in acidic
medium for QN, BN, and CE respectively. High chemical reactivity and
low kinetic stability are general features of a molecule with low energy
gap [42], and as such the order of corrosion inhibition efficiency in sul-
furic acid medium is expected to be QN N BN N CE.
Dipole moment (μ) is another crucial parameter that is well corre-
lated with inhibition efficiency of a molecule in the literature
[22,26,52]. All the studied compounds show greater dipole moment
than that of water (1.88 Debye) to suggest possibly strong dipole-
dipole interactions between each molecule and metal surface [55]. Im-
portantly, these three compounds show better charge separation in
acidic solution than in gas phase to suggest better intra-molecular inter-
ð12Þ dium. Intuitively, the protonation of these compounds in acidic medium
ð13Þ with the observed changes in structural geometries and total negative
charges (TNC) of these compounds to further show the solvent effects.
The TNC values quantitatively describe the adsorption sites in an inhib-
itor molecule such that a high value of TNC signifies a strong adsorption
of the inhibitor molecule on a metal surface. Accordingly, the proton-
ation site was found to be O1 for QN (this agrees with what is reported
for a structurally similar compound, xanthone [56]), O4 for BN, and N18
for CE. The QN, BN, and CE have −3.070e, −6.940e, and − 7.605e re-
spectively for TNC values in gas phase as compared to −3.465e,
−7.496e, and − 7.925e respectively in acid medium (Table 2). Alto-
gether, the high TNC, high dipole moment, and low energy gap facilitate
electron transfer to the metal through adsorption.
Table 3 summarizes the values obtained for other derived quantum
chemical descriptors. The corrected HOMO values correctly predicts
ionization potential (IP) using Koopman's theorem, mathematically
expressed in Eq. (1). The same trend is observed with respect to ioniza-
tion potential and electron affinity which are basic descriptors of chem-
ical reactivity. The IP values are of 5.534 eV, 5.706 eV, and 6.615 eV for

Table 2
Chemical reactivity indices obtained for the studied compounds in neutral forms using the Table 3
DFT-B3LYP/6-311G++(d,p) level of theory. Quantum chemical descriptors derived for the studied compounds in neutral forms at
DFT-B3LYP/6-311G++(d,p) level of theory.
Compound Medium EHOMO ELUMO ΔEL-H μ Relative TNC
(eV) (eV) (eV) (Debye) energy (e) Compound Medium IP EA η χ ρ ω ΔN
(au) (eV) (eV) (eV) (eV) (eV−1) (eV)

CE G −6.804 −2.086 4.718 4.538 0.000 −7.605 CE G 6.804 2.086 2.359 4.445 0.424 4.188 0.080
A −6.615 −1.707 4.908 6.695 0.040 −7.925 A 6.615 1.707 2.454 4.161 0.407 3.528 0.134
QN G −5.654 −3.328 2.326 4.132 0.000 −3.070 QN G 5.654 3.328 1.163 4.491 0.860 8.671 0.141
A −5.534 −3.211 2.323 6.034 0.025 −3.465 A 5.534 3.211 1.162 4.373 0.861 8.230 0.193
BN G −5.917 −3.302 2.615 2.317 0.000 −6.940 BN G 5.917 3.302 1.308 4.610 0.765 8.125 0.081
A −5.706 −3.272 2.434 3.027 0.042 −7.496 A 5.706 3.272 1.217 4.489 0.822 8.279 0.136

Note: ‘G’ represents gas phase and ‘A’ represents acidic medium. Note: ‘G’ represents gas phase and ‘A’ represents acidic medium.
 K.O. Sulaiman et al. / Journal of Molecular Liquids 279 (2019) 342–350 347

Fig. 4. Electrostatic potential (ESP) maps and Mulliken charges for CE, QN, and BN compounds in H2SO4 medium.

QN, BN, and CE respectively in acidic medium. These lower values of IP shows high reactivity and thus has better inhibition efficiency [57]. All
suggest better reactivity than in gaseous phase. In accordance with the compounds show lower electronegativity in acidic medium to indi-
Sanderson's principle of electronegativity equalization, a compound cate their better corrosion inhibition properties in spite of acidic envi-
with low electronegativity assumes equalization less rapidly and ronment. Their constituent heteroatoms have electron donating

Table 4
Condensed Fukui Functions obtained for the studied compounds.

Compound Atom Medium P(N) P(N + 1) P(N-1) f−

k f+
k f0k

G −0.831 −0.851 −0.785 0.020 0.046 0.033

N-1
A −0.855 −0.938 −0.756 0.082 0.100 0.091
G −0.664 −0.671 −0.544 0.006 0.121 0.064
N-6
A −0.660 −0.716 −0.350 0.056 0.310 0.183
G −0.825 −0.848 −0.598 0.022 0.228 0.125
N-18
A −0.871 −0.869 −0.719 −0.002 0.152 0.101
CE
G −0.655 −0.680 −0.425 0.025 0.230 0.127
O-5
A −0.725 −0.730 −0.609 0.005 0.116 0.061
G −0.696 −0.727 −0.663 0.031 0.034 0.032
O-24
A −0.694 −0.697 −0.682 0.002 0.012 0.007
G −0.615 −0.632 −0.489 0.018 0.126 0.072
O-25
A −0.645 −0.644 −0.596 −0.002 0.049 0.024
G −0.470 −0.506 −0.450 0.020 0.036 0.028
O-1
A −0.470 −0.511 −0.432 0.038 0.041 0.040
G −0.667 −0.765 −0.617 0.050 0.098 0.074
O-4
A −0.695 −0.705 −0.331 0.365 0.009 0.187
G −0.683 −0.724 −0.633 0.050 0.041 0.045
O-18
A −0.715 −0.741 −0.674 0.041 0.026 0.034
G −0.673 −0.702 −0.641 0.032 0.029 0.030
QN O-19
A −0.691 −0.767 −0.746 −0.055 0.076 0.010
G −0.696 −0.722 −0.625 0.071 0.027 0.049
O-20
A −0.717 −0.755 −0.723 −0.007 0.039 0.016
G −0.679 −0.713 −0.607 0.072 0.034 0.053
O-21
A −0.703 −0.766 −0.743 −0.040 0.063 0.012
G −0.717 −0.736 −0.681 0.037 0.019 0.028
O-22
A −0.739 −0.764 −0.748 −0.009 0.025 0.008
G −0.540 −0.564 −0.493 0.024 −0.493 0.035
O-1
A −0.547 −0.568 −0.542 0.020 0.005 0.013
G −0.575 −0.714 −0.509 0.140 −0.509 0.103
O-2
A −0.614 −0.765 −0.597 0.151 0.017 0.084
BN
G −0.660 −0.698 −0.605 0.038 −0.605 0.047
O-3
A −0.676 −0.702 −0.673 0.026 0.003 0.014
G −0.541 −0.557 −0.438 0.016 −0.438 0.060
O-4
A −0.553 −0.557 −0.391 0.004 0.162 0.083

Note: ‘G’ represents gas phase while ‘A’ represents acidic medium.
348 K.O. Sulaiman et al. / Journal of Molecular Liquids 279 (2019) 342–350
Table 5
Binding and interaction energies of green inhibitors adsorbed on Fe (110) surface in the
presence of corrosion species.
Compounds Ebinding (kcal/mol) Einteraction (kcal/mol)
CE 539.23 −539.23
QN 570.95 −570.95
BN 563.96 −563.96
potential to account for their relative electropositivity which is empha-
sized with the notable colours that appear in their electrostatic potential
map (Fig. 4). The electrostatic potential decreases in the order of blue,
green, orange, and red [26].
The stabilization of a molecular system when electron is received
from environment is estimated as the global electrophilicity index
(ω), and its high value indicates a good electrophilicity of a compound
and vice versa [58]. A corrosion inhibitor is expected to be a good nucle-
ophile rather than being an electrophile, and the greater nucleophilicity
observed for each of the three studied compounds in sulfuric acid me-
dium than in gas phase indicates their lower propensities to accept elec-
tron from metal, and thus further corroborates their corrosion inhibition
effects. In fact, the protonation in acidic medium will create more
atomic sites on a compound for electrophilic attack by the metal to be
protected from corroding (i.e. dissolving). Furthermore, heteroatoms
with negative charges are regarded as binding sites to the metal surface
by Mulliken charges analysis (Figs. 4 and S2) such that more electrons
are donated to the empty orbital of metal by the site with greater nega-
tive charges [41]. All studied compounds show greater negative charges
on their constituent heteroatoms in acidic medium and their TNC values
follow the same trend. This observation like other global chemical de-
scriptors reflects the stabilization effect of the sulfuric acid solution to
support decrease in individual molecular energies compared to in gas
phase (Table S1).
The work function (ϕ) of a metal surface has been reported as the
mostly correct parameter to be used, instead of electronegativity (χ),
Fig. 5. Adsorption of CE, QN, and BN compounds onto Fe (110) surface in H2SO4 medium.
in estimating ΔN, and 3.88 eV, 3.91 eV, and 4.82 eV are ϕ values ob-
tained for Fe (111), Fe (100), and Fe (110) surfaces respectively, from
DFT calculations [39,59]. In this study, ϕ value of 4.82 eV was used to es-
timate ΔN for each compound because Fe (110) surface, as the most sta-
ble, was chosen in this study. According to Lukovits et al., the amount of
electron transferred from inhibitor molecule to metal atom (ΔN) can be
used to rank the extent of inhibiting metal dissolution for any system of
ΔN b 3.6 [60]. While positive value of ΔN suggests electron transfer from
molecule to metal, negative value indicates electron transfer in reverse
direction [39,61]. The three compounds QN, BN, and CE have greater
positive values for ΔN in acidic medium than in gas phase to suggest
their efficacies against metal corrosion in acidic medium. The QN, BN,
and CE have ΔN values of 0.193, 0.136, and 0.134 respectively in sulfuric
acid environment, and this trend agrees with results obtained for order
of electron donating ability at metal surface to corroborate their corro-
sion inhibition effects.
Tables S2 and S3 present results obtained for chemical reactivity
indices and quantum chemical descriptors respectively, for proton-
ated forms of these compounds. Although almost similar trends can
be observed, values are significantly different from those reported
for neutral forms, and the solution effects are more obvious, with
much differences in values for gas phases and acidic media. Notably,
ΔN values are mostly negative (Table S3), unlike in the case of neu-
tral forms, and this indicates that electrons are transferred from
metal to these molecules when in protonated forms. In other
words, it can be said that protonated forms of these compounds
show greater propensities to accept electron from metal, and this be-
havior will lessen their corrosion inhibition effects, in comparison
with neutral molecules.
By extension, Fukui indices can be used to determine the active sites
of an inhibitor compound and its function entails using local descriptors
to theoretically justify the HSAB principle [62,63]. The natural popula-
tion analysis and estimated Fukui functions for QN, BN, and CE are sum-
marized in Table 4. This gives information about the most probable site
for electrophilic or nucleophilic attack on the molecule. Specifically, the
preferred site for electrophilic attack has the highest value for f− while
 K.O. Sulaiman et al. / Journal of Molecular Liquids 279 (2019) 342–350
that for nucleophilic attack has the highest value for f+. The largest f−
and f+ values occur both on the O4 atom for QN, on O2 and O4 respec-
tively for BN, and on N1 and N6 atoms respectively for CE.
The MD simulations were conducted to further gain insight into the
interaction between these green corrosion inhibitors and metal surface.
At first, the energy of each Fe surface was calculated and found to follow
the trend: E(111) N E(100) N E(110) while stabilities of Fe surfaces increase
with their packing densities: Fe (111) b Fe (100) b Fe (110), in agree-
ment with trend reported in literature [39,64,65]. The densely packed
Fe (110) surface with most stabilization energy, together with other en-
tities like H2O, H3O+, and SO42−, that could participate in the sulfuric
acid based corrosion process were put into consideration during subse-
quent simulation studies. At the equilibrium state of dynamic simula-
tions, the actual interfacial configuration of the surface adsorbed
inhibitor can be obtained, as well as the binding energy using Eq. (10).
Table 5 summarizes the binding energy (Ebinding) and interaction energy
(Einteraction) values obtained while Fig. 5 shows the optimized adsorp-
tion configurations of the green inhibitors over the Fe (110) surface, in
the presence of other corrosion species. These inhibitors possess poten-
tial binding sites as shown in results from the quantum chemical calcu-
lations. The constituent heteroatoms and π systems can bind to the
metal surface either by back bonding from the d-orbital of the metal
or coordinate bond with vacant d-orbitals of the metal. The values ob-
tained for Einteraction are negative and these indicate that the studied in-
hibitors adsorbed on the Fe (110) surface spontaneously [53]. QN shows
almost parallel or flat orientations, but such completely flat orientations
is prevented in BN and CE molecules, perhaps due to the spatial orienta-
tion of anchoring moieties. The degree of flat orientation corresponds to
extent of interaction between the inhibitor molecule and the metal sur-
face. The more stable inhibitor-surface interaction, the greater the bind-
ing energy and thus, the better the corrosion inhibition performance.
The order of increase in binding energy is QN (570.95 kcal/mol) N BN
(563.96 kcal/mol) N CE (539.23 kcal/mol) and this suggests QN pos-
sesses better inhibition performance against acidic attack than BN,
which is also better than CE. This same trend is observed with respect
to quantum chemical parameters that are well correlated with corro-
sion inhibition performance. Altogether, results from these computa-
tional studies are in good agreement with the inhibition efficiencies
reported experimentally.
4. Conclusion
Quantum chemical calculations and molecular dynamic simulations
facilitated molecular level understanding of the mild steel corrosion in-
hibitions by green compounds: CE, QN, and BN. The molecular proper-
ties of these compounds from quantum chemical calculations are well
correlated with the results obtained from both MD simulations studies
and available experimental data. These inhibitors adsorbed to iron sur-
face in sulfuric acid medium spontaneously and the binding energies
were 570.95 kcal/mol, 563.96 kcal/mol, 539.23 kcal/mol for QN, BN,
and CE respectively, in the same order with the extent of flat or parallel
orientation due to the interaction between these inhibitors and metal
surface. The constituent heteroatoms and π systems enabled interaction
with the metal surface either by back bonding from the d-orbital of the
metal or coordinate bond with vacant d-orbitals of the metal. This com-
putational studies complemented experimental results in providing a
better understanding of inhibition of acid-induced corrosion of mild
steel by the studied compounds whose sources are cheap and environ-
mentally friendly.
Acknowledgements
The authors acknowledged the support of the Information Technol-
ogy Centre at King Fahd University of Petroleum and Minerals (KFUPM),
Saudi Arabia, for providing High Performance Computing (HPC) re-
sources used in this research work.
349
Funding
This research did not receive any specific grant from funding agen-
cies in the public, commercial, or not-for-profit sectors.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.molliq.2019.01.136.
References
[1] V.S. Sastri, Green Corrosion Inhibitors: Theory and Practice, First Wiley, NewJersey,
2011.
[2] A.Y. El-etre, Inhibition of C-steel corrosion in acidic solution using the aqueous ex-
tract of zallaouh root, Mater. Chem. Phys. 108 (2008) 278–282.
[3] G. Koch, J. Varney, N. Thompson, O. Moghissi, M. Gould, J. Payer, International Mea-
sures of Prevention, Application, and Economics of Corrosion Technologies Study,
Houston, http://impact.nace.org/documents/Nace-International-Report.pdf 2016.
[4] M. Jeeva, G.V. Prabhu, M. susai Boobalan, C.M. Rajesh, Interactions and inhibition ef-
fect of urea-derived Mannich bases on a mild steel surface in HCl, J. Phys. Chem. C
119 (2015) 22025–22043, https://doi.org/10.1021/acs.jpcc.5b05788.
[5] A. Dandia, S.L. Gupta, P. Singh, M.A. Quraishi, Ultrasound-assisted synthesis of
Pyrazolo[3,4-b]pyridines as potential corrosion inhibitors for mild steel in 1.0M
HCl, ACS Sustain. Chem. Eng. 1 (2013) 1303–1310, https://doi.org/10.1021/
sc400155u.
[6] S.E. Manahan, Environmental Chemistry, CRC Press, Boca Raton, 1994.
[7] B.E.A. Rani, B.B.J. Basu, Green inhibitors for corrosion protection of metals and alloys:
an overview, Int. J. Corros. 2012 (2012)https://doi.org/10.1155/2012/380217.
[8] M. Sangeetha, S. Rajendran, T.S. Muthumegala, A. Krishnaveni, Green corrosion
inhibitors-an overview, Zast. Mater. 52 (2011) 3.
[9] D. Kesavan, M. Gopiraman, N. Sulochana, Green inhibitors for corrosion of metals: a
review, Chem. Sci. Rev. Lett. 1 (2012) 1–8.
[10] M.A. Deyab, Corrosion inhibition of aluminum in biodiesel by ethanol extracts of
rosemary leaves, J. Taiwan Inst. Chem. Eng. 58 (2016) 536–541, https://doi.org/10.
1016/J.JTICE.2015.06.021.
[11] S. Javadian, B. Darbasizadeh, A. Yousefi, F. Ektefa, N. Dalir, J. Kakemam, Dye-
surfactant aggregates as corrosion inhibitor for mild steel in NaCl medium: experi-
mental and theoretical studies, J. Taiwan Inst. Chem. Eng. 71 (2017) 344–354,
https://doi.org/10.1016/J.JTICE.2016.11.014.
[12] N. Asadi, M. Ramezanzadeh, G. Bahlakeh, B. Ramezanzadeh, Utilizing Lemon Balm
extract as an effective green corrosion inhibitor for mild steel in 1M HCl solution:
a detailed experimental, molecular dynamics, Monte Carlo and quantum mechanics
study, J. Taiwan Inst. Chem. Eng. (2018)https://doi.org/10.1016/J.JTICE.2018.07.011.
[13] D. Ladha, N. Shah, S. Thakur, M. Lone, P. Jha, Corrosion inhibition and adsorption be-
haviour of black pepper extract on pure aluminum in hydrochloric acid medium: a
combined experimental and computational study, Pigm. Resin Technol. 45 (2016)
106–118, https://doi.org/10.1108/PRT-10-2014-0086.
[14] S. Pathan, S. Ahmad, Synergistic Effects of Linseed Oil Based Waterborne Alkyd and
3-Isocynatopropyl Triethoxysilane: Highly Transparent, Mechanically Robust, Ther-
mally Stable, Hydrophobic, Anticorrosive Coatings, 4, 2016 3062–3075, https://doi.
org/10.1021/acssuschemeng.6b00024.
[15] E.E. Oguzie, K.L. Oguzie, C.O. Akalezi, I.O. Udeze, J.N. Ogbulie, V.O. Njoku, Natural
products for materials protection: corrosion and microbial growth inhibition using
capsicum frutescens biomass extracts, ACS Sustain. Chem. Eng. 1 (2013) 214–225,
https://doi.org/10.1021/sc300145k.
[16] A.M. Rimando, P.M. Perkins-Veazie, Determination of citrulline in watermelon rind,
J. Chromatogr. A 1078 (2005) 196–200, https://doi.org/10.1016/J.CHROMA.2005.05.
009.
[17] N.A. Odewunmi, S.A. Umoren, Z.M. Gasem, S.A. Ganiyu, Q. Muhammad, L-Citrulline:
an active corrosion inhibitor component of watermelon rind extract for mild steel in
HCl medium, J. Taiwan Inst. Chem. Eng. 51 (2015) 177–185, https://doi.org/10.
1016/J.JTICE.2015.01.012.
[18] N.A. Odewunmi, S.A. Umoren, Z.M. Gasem, Watermelon waste products as green
corrosion inhibitors for mild steel in HCl solution, J. Environ. Chem. Eng. 3 (2015)
286–296, https://doi.org/10.1016/j.jece.2014.10.014.
[19] K.M. Hijazi, A.M. Abdel-Gaber, G.O. Younes, Influence of Malus domestica and
Caesalpinia bonducella leaf extracts on the corrosion behaviour of mild steel in
H2SO4 solution, Int. J. Electrochem. Sci. 10 (2015) 4779–4792.
[20] L. Afia, M. Larouj, R. Salghi, S. Jodeh, M. Zougagh, A.R. Hasan, H. Lgaz, Experimental
and theoretical evaluation of quercetin as a novel and eco-friendly corrosion inhib-
itor for C38 steel in hydrochloric medium, Pharma Chem. 8 (2016) 166–179.
[21] C. Verma, H. Lgaz, D.K. Verma, E.E. Ebenso, I. Bahadur, M.A. Quraishi, Molecular dy-
namics and Monte Carlo simulations as powerful tools for study of interfacial ad-
sorption behavior of corrosion inhibitors in aqueous phase: a review, J. Mol. Liq.
260 (2018) 99–120, https://doi.org/10.1016/j.molliq.2018.03.045.
[22] I.B. Obot, D.D. Macdonald, Z.M. Gasem, Density functional theory (DFT) as a power-
ful tool for designing new organic corrosion inhibitors. Part 1: an overview, Corros.
Sci. 99 (2015) 1–30, https://doi.org/10.1016/J.CORSCI.2015.01.037.
[23] M.E. Belghiti, S. Echihi, A. Mahsoune, Y. Karzazi, A. Aboulmouhajir, A. Dafali, I.
Bahadur, Piperine derivatives as green corrosion inhibitors on iron surface; DFT,
Monte Carlo dynamics study and complexation modes, J. Mol. Liq. 261 (2018)
62–75, https://doi.org/10.1016/J.MOLLIQ.2018.03.127.
350 K.O. Sulaiman et al. / Journal of Molecular Liquids 279 (2019) 342–350
[24] H. Allal, Y. Belhocine, E. Zouaoui, Computational study of some thiophene deriva-
tives as aluminium corrosion inhibitors, J. Mol. Liq. 265 (2018) 668–678, https://
doi.org/10.1016/J.MOLLIQ.2018.05.099.
[25] L.H. Madkour, S. Kaya, I.B. Obot, Computational, Monte Carlo simulation and exper-
imental studies of some arylazotriazoles (AATR) and their copper complexes in cor-
rosion inhibition process, J. Mol. Liq. 260 (2018) 351–374, https://doi.org/10.1016/J.
MOLLIQ.2018.01.055.
[26] K.O. Sulaiman, A.T. Onawole, Quantum chemical evaluation of the corrosion inhibi-
tion of novel aromatic hydrazide derivatives on mild steel in hydrochloric acid,
Comput. Theor. Chem. 1093 (2016) 73–80, https://doi.org/10.1016/j.comptc.2016.
08.014.
[27] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, G.
Scalmani, V. Barone, B. Mennucci, G.A. Petersson, H. Nakatsuji, M. Caricato, X. Li,
H.P. Hratchian, A.F. Izmaylov, J. Bloino, G. Zheng, J.L. Sonnenberg, M. Hada, M.
Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O.
Kitao, H. Nakai, T. Vreven, J.A.J. Montgomery, J.E. Peralta, F. Ogliaro, M. Bearpark,
J.J. Heyd, E. Brothers, K.N. Kudin, V.N. Staroverov, R. Kobayashi, J. Normand, K.
Raghavachari, A. Rendell, J.C. Burant, S.S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J.M.
Millam, M. Klene, J.E. Knox, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R.
Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W.
Ochterski, R.L. Martin, K. Morokuma, V.G. Zakrzewski, G.A. Voth, P. Salvador, J.J.
Dannenberg, S. Dapprich, A.D. Daniels, Ö. Farkas, J.B. Foresman, J.V. Ortiz, J.
Cioslowski, D.J. Fox, Gaussian 09, Revision D.01, Gaussian, Inc., Wallingford CT,
2013https://doi.org/10.1063/PT.4.2023 (M4 – Citavi).
[28] N. Kovačević, A. Kokalj, DFT study of interaction of azoles with Cu(111) and Al(111)
surfaces: role of azole nitrogen atoms and dipole–dipole interactions, J. Phys. Chem.
C 115 (2011) 24189–24197, https://doi.org/10.1021/jp207076w.
[29] A.V. Marenich, C.J. Cramer, D.G. Truhlar, Universal solvation model based on solute
electron density and on a continuum model of the solvent defined by the bulk di-
electric constant and atomic surface tensions, J. Phys. Chem. B 113 (2009)
6378–6396, https://doi.org/10.1021/jp810292n.
[30] B. Mennucci, R. Cammi, Continuum Solvation Models in Chemical Physics: From
Theory to Applications, 2007https://doi.org/10.1002/9780470515235.
[31] C.J. Cramer, Essentials of Computational Chemistry: Theories and Models, Second
John Wiley & Sons, West Sussex, England, 2004https://doi.org/10.1016/B978-0-
12-374507-1.00050-9.
[32] J. Foresman, Æ. Frisch, Exploring Chemistry With Electronic Structure Methods,
Pittsburgh, 1995.
[33] J. House, K. House, Descriptive Inorganic Chemistry, Second Elsevier Inc., San Diego,
California, 2010https://doi.org/10.1017/CBO9781107415324.004.
[34] H.P.R. Frederiske, Dielectric measurements, in: T.F. Connolly (Ed.), Electr. Prop.
Solids, First EditPlenum Press, London 1972, pp. 85–147, https://doi.org/10.1007/
978-1-4684-8607-0_4.
[35] G. Burbidge, C. Wickramasinghe, J. Narlikar, Fred Hoyle's Universe, Springer Science
Business Media, 2003https://doi.org/10.1007/978-94-017-1605-5.
[36] J. Sánchez-Márquez, D. Zorrilla, A. Sánchez-Coronilla, D.M. de los Santos, J. Navas, C.
Fernández-Lorenzo, J. Martín-Calleja, R. Alcántara, Introducing “UCA-FUKUI” soft-
ware: reactivity-index calculations, J. Mol. Model. 20 (2014) 1–13, https://doi.org/
10.1007/s00894-014-2492-1.
[37] M. Rarey, B. Kramer, T. Lengauer, G. Klebe, A fast flexible docking method using an
incremental construction algorithm, J. Mol. Biol. 261 (1996) 470–489, https://doi.
org/10.1006/jmbi.1996.0477.
[38] G. Gece, S. Bilgic, A theoretical study of some hydroxamic acids as corrosion inhibi-
tors for carbon steel, Corros. Sci. 5 (2010) 3304–3308.
[39] L.H. Madkour, L. Guo, C. Kaya, Quantum chemical calculations, molecular dynamic
(MD) simulations and experimental studies of using some azo dyes as corrosion in-
hibitors for iron. Part 2: bis-azo dye derivatives, J. Mol. Struct. 1163 (2018) 397–417,
https://doi.org/10.1016/j.molstruc.2018.03.013.
[40] M. Yadav, D. Behera, S. Kumar, R.R. Sinha, Experimental and quantum chemical
studies on the corrosion inhibition performance of benzimidazole derivatives for
mild steel in HCl, Ind. Eng. Chem. Res. 52 (2013) 6318–6328, https://doi.org/10.
1021/ie400099q.
[41] R.S. Mulliken, Electronic population analysis on LCAO-MO molecular wavefunctions,
J. Chem. Phys. 23 (1955) 1833–1840.
[42] I.B. Obot, Z.M. Gasem, Theoretical evaluation of corrosion inhibition performance of
some pyrazine derivatives, Corros. Sci. 83 (2014) 359–366, https://doi.org/10.1016/
j.corsci.2014.03.008.
[43] L. Guo, I.B. Obot, X. Zheng, X. Shen, Y. Qiang, S. Kaya, C. Kaya, Theoretical insight into
an empirical rule about organic corrosion inhibitors containing nitrogen, oxygen,
and sulfur atoms, Appl. Surf. Sci. 406 (2017) 301–306, https://doi.org/10.1016/j.
apsusc.2017.02.134.
[44] N.A. Wazzan, I.B. Obot, S. Kaya, Theoretical modeling and molecular level insights
into the corrosion inhibition activity of 2-amino-1,3,4-thiadiazole and its 5-alkyl de-
rivatives, J. Mol. Liq. 221 (2016) 579–602, https://doi.org/10.1016/J.MOLLIQ.2016.
06.011.
[45] S.W. Bunte, H. Sun, Molecular modeling of energetic materials: the parameterization
and validation of nitrate esters in the COMPASS force field, J. Phys. Chem. B 104
(2000) 2477–2489, https://doi.org/10.1021/jp991786u.
[46] J. Yang, Y. Ren, A. Tian, Compass force field for 14 inorganic molecules, He, Ne, Ar, Kr,
Xe, H2, O2, N2, NO, CO, CO2, NO2, CS2, and SO2, in liquid phases, J. Phys. Chem. B 104
(2000) 4951–4957, https://doi.org/10.1021/jp992913p.
[47] G. Liu, S. Chen, H. Ma, X. Liu, Molecular simulation study of 1,5-diphenylcarbazide
self-assembled monolayers on a copper surface, J. Serb. Chem. Soc. 72 (2007)
475–484, https://doi.org/10.2298/JSC0705475L.
[48] M. Sathyadevi, S. Subramanian, Extraction, isolation and characterization of bioac-
tive flavonoids from the fruits of Physalis peruviana Linn extract, Asian J. Pharm.
Clin. Res. 8 (2015) 152–157.
[49] H. Allouchi, B. Nicolaï, M. Barrio, R. Céolin, N. Mahé, J.L. Tamarit, B. Do, I.B. Rietveld,
On the polymorphism of l-citrulline: crystal structure and characterization of the or-
thorhombic δ form, Cryst. Growth Des. 14 (2014) 1279–1286, https://doi.org/10.
1021/cg401801u.
[50] M. Rossi, L.F. Rickles, W.A. Halpin, The crystal and molecular structure of quercetin: a
biologically active and naturally occurring flavonoid, Bioorg. Chem. 14 (1986)
55–69, https://doi.org/10.1016/0045-2068(86)90018-0.
[51] S.-L. Ng, I.A. Razak, H.-K. Fun, S. Boonsri, S. Chantrapromma, U. Prawat, 1,3-Dihy-
droxy-2-methyl-9,10-anthraquinone, Acta Crystallogr., Sect. E: Struct. Rep. Online
61 (2005) o3656–o3658, https://doi.org/10.1107/S1600536805031697.
[52] Z. El Adnani, M. Mcharfi, M. Sfaira, M. Benzakour, A.T. Benjelloun, M. Ebn Touhami,
DFT theoretical study of 7-R-3methylquinoxalin-2(1H)-thiones (RH; CH3; Cl) as
corrosion inhibitors in hydrochloric acid, Corros. Sci. 68 (2013) 223–230, https://
doi.org/10.1016/j.corsci.2012.11.020.
[53] S.K. Saha, A. Dutta, P. Ghosh, D. Sukul, P. Banerjee, Novel Schiff-base molecules as ef-
ficient corrosion inhibitors for mild steel surface in 1 M HCl medium: experimental
and theoretical approach, Phys. Chem. Chem. Phys. 18 (2016) 17898–17911,
https://doi.org/10.1039/C6CP01993E.
[54] G. Zhang, C.B. Musgrave, Comparison of DFT methods for molecular orbital eigen-
value calculations, J. Phys. Chem. A 111 (2007) 1554–1561, https://doi.org/10.
1021/jp061633o.
[55] B.D. Mert, M. Erman Mert, G. Kardaş, B. Yazıcı, Experimental and theoretical investi-
gation of 3-amino-1,2,4-triazole-5-thiol as a corrosion inhibitor for carbon steel in
HCl medium, Corros. Sci. 53 (2011) 4265–4272, https://doi.org/10.1016/J.CORSCI.
2011.08.038.
[56] I. Obot, N.O. Obi-Egbedi, Anti-corrosive properties of xanthone on mild steel corro-
sion in sulphuric acid: experimental and theoretical investigations, Curr. Appl. Phys.
11 (2011) 382–392.
[57] R.T. Sanderson, Chemical Bonds and Bond Energy, Academic, New York, 1976.
[58] R.G. Parr, L.V. Szentpály, S. Liu, Electrophilicity index, J. Am. Chem. Soc. 121 (1999)
1922–1924, https://doi.org/10.1021/ja983494x.
[59] A. Kokalj, On the HSAB based estimate of charge transfer between adsorbates and
metal surfaces, Chem. Phys. 393 (2012) 1–12, https://doi.org/10.1016/J.
CHEMPHYS.2011.10.021.
[60] I. Lukovits, E. Kalmán, F. Zucchi, Corrosion inhibitors correlation between electronic
structure an efficiency, Corrosion 57 (2001) 3–8.
[61] Y. Xu, S. Zhang, W. Li, L. Guo, S. Xu, L. Feng, L.H. Madkour, Experimental and theoret-
ical investigations of some pyrazolo-pyrimidine derivatives as corrosion inhibitors
on copper in sulfuric acid solution, Appl. Surf. Sci. 459 (2018) 612–620, https://
doi.org/10.1016/j.apsusc.2018.08.037.
[62] K. Fukui, Role of frontier orbitals in chemical reactions, Science 218 (1982) 747–754
(80-. ).
[63] A. Kokalj, N. Kovačević, On the consistent use of electrophilicity index and HSAB-
based electron transfer and its associated change of energy parameters, Chem.
Phys. Lett. 507 (2011) 181–184, https://doi.org/10.1016/J.CPLETT.2011.03.045.
[64] L. Vitos, A.V. Ruban, H.L. Skriver, J. Kollár, The surface energy of metals, Surf. Sci. 411
(1998) 186–202, https://doi.org/10.1016/S0039-6028(98)00363-X.
[65] A. Arya, E.A. Carter, Structure, bonding, and adhesion at the TiC(100)/Fe(110) inter-
face from first principles, J. Chem. Phys. 118 (2003) 8982–8996, https://doi.org/10.
1063/1.1565323.