Applied Surface Science 256 (2010) 47294733

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Applied Surface Science

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

Molecular modeling study on inhibition performance of imidazolines for mild

steel in CO2 corrosion
Jinxiang Liu a , Weizhao Yu b , Jun Zhang a, , Songqing Hu a , Long You a , Guimin Qiao a
a
College of Physics Science and Technology, China University of Petroleum, Beier Road 271, Dongying, Shandong 257061, PR China
b
College of Petroleum Engineering, China University of Petroleum, Qingdao, Shandong 266555, PR China

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

Article history: Corrosion inhibiting performance of 1-hydroxyethyl-2-heptadecylimidazoline (A) and 1-aminoethyl-2-

Received 9 November 2009 heptadecylimidazoline (B) for mild steel was evaluated by combination of quantum chemistry calculation,
Received in revised form 22 February 2010 molecular mechanics, and molecular dynamics simulation. The calculated results by quantum chemistry
Accepted 26 February 2010
method demonstrated that frontier orbitals of A and B molecules are mainly located on imidazoline rings,
Available online 4 March 2010
and molecule B possesses higher reactivity than molecule A. The calculated results by molecular mechan-
ics and molecular dynamics simulation presented that these two inhibitor molecules could form dense
Keywords:
and high-coverage membranes to prevent diffusion of reactive corrosive species to metal surface. Fur-
Imidazoline
Corrosion inhibitor
thermore, the adsorption energy, cohesive energy, and adsorption angle demonstrated that the binding
Molecular modeling afnity and stability of B membrane was remarkably greater than that of A, which indicated that B had
better inhibition performance in CO2 corrosion. The calculated results were well accorded with previous
reported experimental results. These researches implied that molecular modeling might be an effective
approach to assess inhibition performance, which has potential application in design of new inhibitors.
2010 Elsevier B.V. All rights reserved.

1. Introduction tions between molecular structures and inhibition efciencies,

Corrosion prevention is an important issue for industrial
application of materials. Among numerous corrosion prevention
measures, corrosion inhibitor, bearing advantages of economy,
high-efciency, and facile-feasibility, have been widely applied
in various elds. In recent years, with improved recognition of
environmental protection, development of new green corrosion
inhibitors has received increasing attention [13]. However, tra-
ditional methods for developing corrosion inhibitors are based on
large-scale trial-and-error experiments, which bring along high-
cost, long-cycle, and have certain blindness. Therefore, theoretical
research is urgently demanded to guide the experimental design
and synthesis.
With the improvement of hardware and software, computer
simulation has become a powerful tool to investigate complex
systems. Through investigation of structure, electron distribu-
tion, and adsorption process of molecules, inhibition mechanism
has been deeply explored. In 1971, Vosta introduced quantum
chemistry methods to investigate corrosion inhibition mechanism
and founded quantum corrosion electrochemistry [4]. Thereafter,
the focus of quantum chemistry method was mainly on rela-
Corresponding author.
E-mail address: zhjupc@yahoo.com (J. Zhang).
and many valuable results have been reported. In the 1990s,
researchers turned their interests to the interaction between
inhibitor molecules and metal surfaces via molecular dynamics
simulation. Sein et al. did much signicant work about the adsorp-
tion effect of inhibitor molecules on their inhibition performance
[5]. At the end of 20th century, Ramachandran and Jovancice-
vic studied the self-assembled monolayer of oleic imidazoline on
carbon steel surface using molecular mechanics method, which
was helpful to understand inhibition mechanism [6]. Recently,
the research hotspot of inhibition mechanism has been shifted
from static state and micro-scale to dynamic state and meso-scale.
Inhibition performance was evaluated through investigating the
inuence of solvent and temperature on adsorption behavior of
inhibitor molecule [7,8]. In general, some valuable results have
been obtained in research of inhibition mechanism and design of
inhibitor molecule, and some methods, including quantum chem-
istry, molecular mechanics and molecular dynamics simulation,
have been introduced into above elds. However, these meth-
ods have their own advantages and shortages in the research of
inhibition mechanism. Among these methods, quantum chemistry
calculation is suitable to deal with static question in small systems,
and molecular mechanics method is preferable to investigate static
congurations of large and complex systems. As for the dynamic
states of complex systems, molecular dynamics simulation exhibits
distinguished advantages. Obviously, it would be facile and effec-
tive to obtain more detailed information by combination of these

0169-4332/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2010.02.082
4730 J. Liu et al. / Applied Surface Science 256 (2010) 47294733
Fig. 1. Optimized geometries and selected structural parameters (in and degree) for 1-hydroxyethyl-2-heptadecylimidazoline (A) and 1-aminoethyl-2-
heptadecylimidazoline (B) evaluated at BLYP/DNP level.
three methods, and provide a new research approach in explo-
ration of inhibition mechanism. Based on above research idea, in
this article, the inhibition performance of one kind of imidazoline
derivatives with different pendant chains was systemically inves-
tigated via above three methods.
Imidazoline derivatives, a kind of environmental-friendly cor-
rosion inhibitors, can effectively inhibit metals corrosion in CO2
environment [6,911]. This property can be ascribed to their
unique structures, which include imidazoline ring, long alkyl
chain, and pendant chain. Previous researches mostly focus
on the investigation of effect of alkyl chain length on inhibi-
tion performance. However, related researches about pendant
chain are scarce, and the inhibition mechanism is still unclear.
In this article, the inhibition performance of two imidazoline
derivatives with different pendant chains in CO2 corrosion envi-
ronment is studied via quantum chemistry, molecular dynamics
simulation, and molecular mechanics methods. Theoretical sim-
ulations derived results in comparison of inhibition performance
of the two compounds were veried by reported experimental
results [12]. This implies that our proposed theoretical method
might be an effective approach to assess the inhibition per-
formance of inhibitor molecule with different pendant chains,
and has potential application in design of environmental-friendly
inhibitor.
2. Calculation
The generalized gradient approximation (GGA) within the den-
sity functional theory was conducted with the software package
DMol3 in Materials Studio of Accelrys Inc. All calculations were
performed using the BeckeLeeYangParr (BLYP) exchange corre-
lation functional and the double numerical with polarization (DNP)
basis set, since this was the best set available in DMol3 . A Fermi
smearing of 0.005 hartree and a real space cutoff of 3.7 was cho-
sen to improve the computational performance. All computations
were performed with spin polarization. Fukui index was also ana-
lyzed to obtain detailed information about the local reactivity [13].
The Fukui function fk is dened as the rst derivative of the elec-
tronic density (r) with respect to the number of electrons N in a
constant external potential v(r) [14]:
 
(r)
fk = (1)
N
v(r)
Applying nite difference approximation, the Fukui functions can
be written as [15]:
fk+ = qk (N + 1) qk (N) (for nucleophilic attack) (2)
fk = qk (N) qk (N 1) (for electrophilic attack) (3)
Herein, qk (N + 1), qk (N), and qk (N 1) are dened as the atomic
charges of the anionic, neutral, and cationic species, respectively.
The Fukui functions were obtained through the nite difference
approximation using Hirschfeld population analysis (HPA) [16].
During the corrosion of mild steel in CO2 environment, FeCO3 ,
Fe3 O4 , and Fe2 O3 can be found in corrosion product lms [17,18].
Many studies show that FeCO3 was the main corrosion product
of mild steel in ow CO2 saturated solutions [19,20]. So, in our
research, FeCO3 was selected as the adsorption surface. For FeCO3
crystal, the (0 0 1) plane is the most stable plane, and was chosen
for study [21]. Firstly, a FeCO3 slab (32.84 32.84 ) terminated
with Fe2+ ions with a thickness of 16.67 was built. And then, the
interaction between inhibitor molecules and FeCO3 surface was
analyzed by molecular dynamics simulation. During simulation, all
the atoms in the FeCO3 surface systems were kept frozen, and the
inhibitor molecules were allowed to interact with the metal surface
freely. The simulation time was 500 ps with a time step of 1 fs. The
simulation temperature was set at 323 K, and the temperature was
controlled by Andersen thermostat. Van der Waals and Coulomb
interactions were calculated by group based method with a cutoff
radius of 15.0 .
Binding energy is an important factor to characterize the adsorp-
tion ability of an inhibitor molecule onto the FeCO3 surface, which
could be calculated by following equation [2,22]:
Ebinding = (Einhibitor + Esurface ) Etotal (4)
In above equation, Einhibitor , Esurface , and Etotal represent the energy
of single molecule, FeCO3 surface without adsorption, and total
system containing a molecule and metallic surface, respectively.
 J. Liu et al. / Applied Surface Science 256 (2010) 47294733 4731

The self-assembled monolayer (SAM) formed by inhibitor

molecules on FeCO3 surface was investigated with molecular
mechanics method. Firstly, a unit cell was built consisting of a FeCO3
slab (8.12 8.12 64.10 ) on which one inhibitor molecule was
placed perpendicularly. Using this unit cell, a simulation system
(4 4) containing 16 inhibitor molecules was built. After the origi-
nal geometrical construction, the structure of three-dimensional
simulated system was optimized using the Smart Minimizer
method in Materials Studio software under COMPASS force eld
[23,24].
The stability of SAM of inhibitor molecules on FeCO3 surface was
analyzed by its cohesive energy calculated by following equation:
isolated periodic
Ecohesive = Enb Enb (5)
periodic
isolated , and E
Herein, the Ecohesive , Enb nb
represent the cohesive
energy of the monolayer, the energy of one isolated inhibitor Fig. 2. Highest occupied molecular orbital with a value of isosurface of
molecule and the energy of one inhibitor molecule in the mono- 0.02 a.u. for 1-hydroxyethyl-2-heptadecylimidazoline (A) and 1-aminoethyl-2-
heptadecylimidazoline (B) evaluated at the BLYP/DNP level of theory.
layer, respectively.

3. Results and discussion

3.1. Geometries of inhibitor molecules

Optimized geometries of the inhibitor molecules A and B are

shown in Fig. 1. The molecules reach their respective ground
state through vibrational frequency calculations. It can be seen
that the pedant chain has little inuence on the conguration
of imidazoline ring. The bond lengths and bond angles of the
imidazoline rings in both A and B molecule are in the range of
1.291.55 and 101.2116.1 , respectively, which are in accor-
dance with reported results (bond length: 1.281.54 ; bond angle:
101.1116.2 ) [2527]. The 1N2C bond length is 1.41 , which is
a typical single bond, and a double bond is formed between 2C
and 3N with bond length of 1.29 . The IR wave numbers of char-
acteristic C(2)N(3) double bonds for molecule A and molecule
B was 1601 cm1 and 1599 cm1 , respectively, while the calcu- Fig. 3. Lowest unoccupied molecular orbital with a value of isosurface of
0.02 a.u. for 1-hydroxyethyl-2-heptadecylimidazoline (A) and 1-aminoethyl-2-
lated IR wave numbers have certain uncertainties [28] of 40 cm1
heptadecylimidazoline (B) evaluated at the BLYP/DNP level of theory.
resulting from DFT calculation. Those values were close to the
experimental values (16001610 cm1 ) [9]. The agreement of
experimental and calculated results veried the validity of these Calculated Fukui indices for molecules A and B are presented
calculated results. in Table 1. Only the largest Fukui indices are quoted. It could be
seen that the largest values of fk locate on the 1N and 3N atoms
3.2. Molecular reactivity for both molecules, which indicates that these two atoms prefer
to donate electrons to metal surfaces and form chemical bonds.
According to frontier orbital theory, the reaction of reactants While the largest values of fk+ are located on the 2C and 3N atoms,
mainly occurred on the highest occupied molecular orbital (HOMO) which suggests that 2C and 3N atoms facilitate to accept electrons
and lowest unoccupied molecular orbital (LUMO) [29]. The HOMO from metal surfaces and form back-donating bonds. However, the
and LUMO distributions of A and B are shown in Figs. 2 and 3. It Fukui indices of 1N, 2C, and 3N atoms increase when the hydroxyl
can be found that both molecules have similar frontier orbital dis- group is replaced by an amido group, which means that molecule B
tribution, and the active reaction zones are mainly located on the has higher capability of electron-donating and electron-accepting,
imidazoline ring, which means that the imidazoline ring would be and could be adsorbed more strongly on the metal surface. As a
preferentially adsorbed onto metal surface by following two fash-
ions: the one was that the unoccupied d orbitals of Fe atom accepted Table 1
electrons of inhibitor molecule to form coordinate bond, the other The Fukui indices of the atoms in imidazoline rings and pendant groups of both A and
was that the inhibitor molecule accepted electrons of Fe atom to B molecules calculated at the PBE/DNP level using Hirschfeld population analysis.

form back-donating bond [30]. Molecule Atom fk+ fk

Experimental researches of RodrguezValdez indicate that the
1N 0.044 0.148
inhibition efciency increases from 88.8% to 96.1% when the 2C 0.156 0.063
hydroxyl group of molecule A was replaced by an amido group to A
3N 0.151 0.169
form molecule B [12]. This point could be validated by the energy of 8O 0.033 0.042
HOMO (EHOMO ) as shown in Fig. 2. From Fig. 2, it could be seen that 1N 0.047 0.151
the EHOMO of molecule B (5.21 eV) is larger than that of molecule 2C 0.162 0.065
B
A (5.38 eV), which indicates that molecule B has better inhibi- 3N 0.154 0.172
8N 0.017 0.021
tion performance than molecule A due to the stronger chemical
adsorption. Only the highest Fukui function values are quoted.
4732 J. Liu et al. / Applied Surface Science 256 (2010) 47294733

Fig. 4. Adsorption conformations of inhibitor molecules on FeCO3 surface for 1-hydroxyethyl-2-heptadecylimidazoline (A) and 1-aminoethyl-2-heptadecylimidazoline (B)
evaluated by molecular dynamics simulation at 323 K.

Fig. 5. The side view of 1-hydroxyethyl-2-heptadecylimidazoline (A) and 1-aminoethyl-2-heptadecylimidazoline (B) monolayer on FeCO3 surface after optimization evalu-
ated by molecular mechanism.

result, molecule B should have higher inhibition performance than
molecule A. This point was in accordance with the experimental
values of inhibition efciency [13].
3.3. Interaction of molecules with FeCO3 surface
The process of metal corrosion is complex and heterogeneous
due to the presence of various anodic and cathodic sties on the
metal surface [6]. For FeCO3 surface, cation Fe2+ presents as an
anodic reactive site, which can bind to electrophilic attacking cen-
ters in inhibitor molecules. Anion CO3 2 presents as a cathodic
reactive center, which can bind to nucleophilic centers in inhibitor
molecules. Therefore, inhibitor molecule can be adsorbed onto the
FeCO3 surface through interaction with these sites, and as a result,
the transport of corrosive species is restricted from solution to
metal surface. Then electrochemical reactions are retarded.
The equilibrium adsorption congurations of molecules A and
B on FeCO3 surface are shown in Fig. 4. From Fig. 4, it could be seen
that both molecules are parallelly adsorbed onto the FeCO3 sur-
face despite of what initial congurations of the inhibitor molecules
take.
During simulation, the imidazoline ring of the molecules is pref-
erentially adsorbed on the FeCO3 surface because of strong charge
transfer effect, which was in accordance with the analysis of distri-
bution of HOMO and LUMO mentioned above. After that, the alkyl
chain will be gradually dragged to the metal surface.
The binding energies of A, B, and H2 O on FeCO3 surface are
84.0, 106.0, and 44.0 kcal/mol, respectively. The binding energy of
molecules A and B are larger than that of H2 O, which indicate that
molecules A and B could displace water molecules and be prefer-
entially adsorbed on metal surface. Comparing with molecule A,
molecule B has larger binding energy and will be adsorbed more
strongly, which imply that molecule B might possess better inhi-
bition performance than molecule A. This point again accords with
experimental results [13].
3.4. Self-assembled monolayer membranes
The inhibitor molecules will form a self-assembled monolayer
after simulation via molecular mechanics. Figs. 5 and 6 present the
side and top views of SAM of molecules A and B. Degree of cover-
age is an important factor to evaluate the inhibition performance
of SAM. From the side view, it can be seen that head groups (imi-
dazoline ring and pendant chain) of inhibitor molecules attach to
FeCO3 surface, and alkyl chains protrude outward with an inclina-
tion against FeCO3 surface. From the top view, it can be seen that
both the metal surface and the absorbed head groups of inhibitor
molecules are covered by alkyl chain, which demonstrates that
molecules A and B all could achieve high degree of coverage on
FeCO3 surfaces. Consequently, the diffusion of corrosive species
from the solution to metal surface would be efciently prevented
by such continuous monolayer.
In addition, the inhibition performance of SAM is further
discussed through investigation of other important factors, i.e.
adsorption angle and cohesive energy. Here the adsorption angle is
dened as the angle between the alkyl chain and the normal direc-
tion of FeCO3 (0 0 1) plane, which was 66.0 and 71.0 for molecules
A and B, respectively.

Fig. 6. The top view of 1-hydroxyethyl-2-heptadecylimidazoline (A) and 1-aminoethyl-2-heptadecylimidazoline (B) monolayer on FeCO3 surface after optimization evaluated
by molecular mechanism.
 J. Liu et al. / Applied Surface Science 256 (2010) 47294733
The larger adsorption angle demonstrates the alkyl chains of
molecules are more closely to the FeCO3 surface, which results
in enhancement of combination between inhibitor molecules and
FeCO3 surface. On the other hand, as the adsorption angle increases,
the distance between the alkyl chains inside the SAM decreases,
which results in stronger van der Waals interaction between these
chains and a more compact and stable SAM will form. This point
can be veried by the calculated cohesive energies of SAM (11.0
and 25.3 kcal/mol for A and B, respectively). Compared with A, the
higher cohesive energy indicates that molecule B can form more
stable SAM on FeCO3 surface. These results mean that the SAM
of molecule B possesses better inhibition efciency than that of
molecule A, which is identical with the experimental results.
4. Conclusions
In this work, molecular modeling was performed
for evaluation of corrosion inhibiting performance of
1-hydroxyethyl-2-heptadecylimidazoline (A) and 1-aminoethyl-
2-heptadecylimidazoline (B) for mild steel in CO2 corrosion
environment. The frontier orbital distributions and Fukui indices
indicated that the reactivity zone of molecules A and B are all
located on imidazoline ring, while molecule B has higher capability
of electron-donating than molecule A, which implies that the
adsorption stability of molecule B is higher than that of molecule
A on metal surface. The larger binding energy of molecule B
demonstrates that molecule B will be adsorbed more strongly
onto the FeCO3 surface than molecule A. In the SAM, the adsorp-
tion angle of molecule B on FeCO3 surface is larger than that of
molecule A, which results in more closely packing of alkyl chain
of molecule B. At the same time, the larger cohesive energy of
molecule B indicates that molecule B can form more stable SAM
on FeCO3 surface. All calculated results reveal that inhibitor B
has better inhibition performance than inhibitor A, which is just
identical with the previously reported experimental results. This
conclusion indicates that our proposed theoretical method might
be an effective approach to assess the inhibition performance of
inhibitor molecule, and has potential applications in design of
newly type inhibitor.
Acknowledgments
This work was nancially supported by Natural Science Foun-
dation of Shandong Province (Y2006B35) and CNPC Innovation
Foundation (07E1021, 2008D-5006-02).
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