Corrosion Science 50 (2008) 20212029

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Molecular dynamics and density functional theory study on relationship

between structure of imidazoline derivatives and inhibition performance
Shuwei Xia *, Meng Qiu, Liangmin Yu, Fuguo Liu, Haizhou Zhao
College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266100, PR China

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

Article history: The inhibition performance of two imidazoline derivatives, 3-ethylamino-2-undecyl imidazoline (EUI)
Received 31 January 2008 and chloride-3-ethylamino-3-(2,3-two hydroxyl) propyl-2-undecyl imidazoline sodium phos-
Accepted 23 April 2008 phate(CEPIP), for Q235 steel in CO2 saturated solution at 298 K have been tested by weight loss experi-
Available online 6 May 2008
ment and electrochemical techniques. The adsorption behavior of the two inhibitors on Fe surface has
been studied using molecular dynamics (MD) method and density functional theory. The results indi-
Keywords: cated that the two imidazoline derivatives could both adsorb on the Fe surface rmly through the imi-
A. Organic coatings
dazoline ring and heteroatoms, the two inhibitors both have excellent corrosion inhibition performance.
B. Modeling studies
C. Acid inhibition
2008 Elsevier Ltd. All rights reserved.
C. Interface

1. Introduction culated a series of p-substituted aniline using semi-empirical

As an economic and effective technique preventing metal and
alloy from being corrupted, inhibitor is widely applied to chemical
cleaning, atmosphere environment, industrial water, machine and
instrument industries, petrochemical engineering production pro-
cess, and become an indispensable protection measure during
industrial production. Nowadays, the synthesis and screening of
inhibitor is carried out mainly in the way of experiments, never-
theless there are few cases to design and synthesize directly
according to the corrosion environment. Therefore, it will offer
important theoretical guidance for the inhibitor designing to study
the relationship between inhibitor structure and inhibition perfor-
mance. For the last decades, quantum chemistry has become an
effective way to study the correlation of the molecular structure
and its inhibition properties and much achievement was reached,
humans knowledge of mechanism of corrosion inhibition pene-
trates to the microscopic level [15]. From the 1970s, Vasta re-
searched the relationship between the quantum chemical
parameters and inhibition efciency using Huckel molecular orbi-
tal theory (HMO) [6]; Costa explained the mechanism of corrosion
inhibition of different linear chain diols, diamines and aliphatic
aminoalcohols using the semi-empirical MINO/3SCF method [7];
Jingchang Zhang calculated the structure of N-contained com-
pounds using HMO method, discovering that the electronic density
and highest occupied molecular orbital (HOMO) energy level of ac-
tive group is in relation to inhibition efciency [8]; Abdul Ahad cal-
* Corresponding author. Tel.: +86 13687632752; fax: +86 532 66782407.
E-mail address: shuweixia@ouc.edu.cn (S. Xia).
CNDO/2 method, and obtained signicant correlations between
corrosion rate and corrosion current with the chemical indexes of
the inhibitors [9]; Daxi Wang calculated the molecular geometry
and chemical adsorption of six imidazolines and Fe atom by MNDO
and CNDO/2M methods, and discussed their inhibition perfor-
mance [10,11]. However, quantum chemistry computing methods,
such as ab initio and semi-empirical methods, are computational
expensive and are usually only applied to systems containing no
more than 100 atoms or small molecules. It is not practical to mod-
el large systems containing dozens of metal atoms and hundreds of
solvent molecules. The molecular dynamics (MD) method is often
used to study the interaction of phase interfaces [1214], only a
few works have been done to research the interaction of inhibitors
with the metal surface [15,16]. Imidazoline is a kind of inhibitor
with high performance, there are few theoretical researches com-
pared with lots of experimental research report [1719].
In the present paper, molecular dynamics and quantum chem-
istry (DFT) are employed to discuss the adsorption conguration,
charge distribution and frontier orbital energy, and to explain the
mechanism of adsorption, thus offering theoretical information of
designing and synthesizing novel inhibitor.
2. Experiments and methods
2.1. Weight loss experiment
Weight loss measurements were carried out using steel speci-
men of size 5 cm  3 cm  1 cm. Q235 steel specimens were im-
mersed in 600 ml of saltwater saturated with CO2, with and

0010-938X/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2008.04.021
2022 S. Xia et al. / Corrosion Science 50 (2008) 20212029

without inhibitors at 298 K for 168 h. The chemical composition of
the saltwater was listed in Table 1. Value of pH of the saltwater sat-
urated with CO2 was 4.86. After that, the specimens were removed,
rinsed water, and nally dried in a desiccator. Then the loss in
weight was determined by analytic balance. The corrosion rate
and inhibition efciency were obtained by
vw W 0  W t =At
IE% W 0  W t =W 0  100%;
where W0 and Wt are the original weight and the weight in the pres-
ence of the inhibitor, respectively, A was the area of specimen and t
is the experimental period.
a representative part of the interface devoid of any arbitrary bound-
ary effects. The box consisted of a Fe slab and a vacuum layer of
2.81 nm height. The Fe crystal was cleaved along the (0 0 1) plane
with the uppermost and the lowest layers released and the inner
layer xed. The MD simulation was performed under 298 K, NVT
ensemble, with a time step of 0.1 fs and simulation time of 50 ps.
The interaction energy EFe-inhibitor of the Fe surface with the inhibitor
1
was calculated according to the following equation:
2

2.2. Potential polarization curves

The potentiodynamic polarization studies were carried out on

Q235 steel strips with an exposed area of 1 cm2 at 298 K. The cell
assembly consisted of Q235 steel as working electrode, a platinum
foil as counter electrode and a saturated calomel electrode (SCE) as
a reference electrode with a Luggin capillary bridge. Polarization
studies were carried out using IM6e (ZAHNER, Germany) electro-
chemistry workstation. The working electrode was immersed in
saltwater saturated with CO2 and allowed to stabilize for 30 min.
The polarization curves for Q235 steel specimen in the saltwater
saturated with CO2 with and without various concentrations of
the inhibitors were recorded at a sweep rate of 1 mV/S. The inhibi-
tion efciencies of the inhibitor were determined from corrosion Fig. 1. Polarization curves of Q235 steel in saltwater saturated with CO2 with va-
currents using the Tafel extrapolation method. rious concentrations of EUI.

2.3. Molecular dynamics simulation

The molecular dynamics (MD) simulations were performed

using the software, Materials Studio. The MD calculation of the
simulation of the interaction between imidazoline derivatives and
the iron surface was carried out in a simulation box (2.009 nm 
0.861 nm  3.444 nm) with periodic boundary conditions to model

Table 1
The chemical composition of the saltwater

Chemical composition Concentration (g/L)

Ca2+ 1.086
Mg2+ 0.224
K+ 0.359
Na+ 9.378
Cl 17.002
SO2
4 0.290
CO3 0.089

Fig. 2. Polarization curves of Q235 steel in saltwater saturated with CO2 with va-
rious concentrations of CEPIP.
Table 2
Corrosion inhibition efciency of the two inhibitors with different concentrations for
Q235 steel in the simulated CO2 saturated solution at 298 K Table 3
Electrochemical parameter obtained from polarization curves
Inhibitor Concentration Corrosion rate Inhibition efciency
(mg/L) (mm/y) (%) Inhibitor Concentration (mg/L) Icorr (mm/y) Inhibition efciency (%)

EUI Blank 0.2631 EUI Blank 1.309

5 0.0478 81.8 5 0.245 81.3
10 0.0355 86.5 10 0.173 86.8
15 0.0275 89.5 15 0.128 90.2
20 0.0215 91.8 20 0.099 92.4
25 0.0183 93.0 25 0.086 93.4

CEPIP Blank 0.2631 CEPIP Blank 1.309

5 0.0460 82.5 5 0.237 81.9
10 0.0335 87.3 10 0.168 87.2
15 0.0260 90.1 15 0.114 91.3
20 0.0199 92.4 20 0.093 92.9
25 0.0168 93.6 25 0.070 94.7
 S. Xia et al. / Corrosion Science 50 (2008) 20212029 2023

EFe-inhibitor Ecomplex  EFe  Einhibitor 3 3. Results and discussion

with Ecomplex being the total energy of the Fe crystal together with
3.1. Weight loss experiment
the adsorbed inhibitor molecule, EFe and Einhibitor being the total en-
ergy of the Fe crystal and free inhibitor molecular, respectively. And
The corrosion inhibition efciency of the two inhibitors with
the binding energy was the negative value of the interaction energy,
various concentrations for Q235 steel in the simulated CO2
Ebinding EFeinhibition . Then, the system was simulated in water
solution with density of 1 g/cm3.
For the whole simulation procedure, the forceeld CVFF was
used. The CVFF (consistent-valence forceeld) was a generalized
valence forceeld tted to small organic, such as amides, carbox-
ylic acids, etc., and metal crystal. It was primarily intended for
studies of structures and bind energies, although it also predicted
vibrational frequencies and conformational energy reasonably
well.

2.4. Quantum chemistry calculation

The quantum chemistry calculations were performed with

Gaussian03 program using B3LYP method [2028] 3-21G(d) basis
set to initially optimize the geometry structure of the two imidaz-
oline derivatives, the optimization was advanced with 6-31G(d)
basis set and the frequency analysis was executed simultaneously,
no imaginary frequency found, indicating that it was a minimum.
The same method and basis set were used to research the structure
and energy of the adsorbed inhibitor molecule after MD simula-
tion, and the active site of the molecule was analyzed.

Fig. 4. CEPIP molecule adsorbed on Fe (0 0 1) surface.

Fig. 3. EUI molecule adsorbed on Fe (0 0 1) surface. Fig. 5. Conguration of EUI molecule adsorbed on Fe (0 0 1) surface.
2024 S. Xia et al. / Corrosion Science 50 (2008) 20212029
Fig. 6. Conguration of CEPIP molecule adsorbed on Fe (0 0 1) surface.
saturated solution at 298 K is shown in Table 2. We can see that
EUI and CEPIP show good inhibition performance for Q235 steel
in simulated CO2 saturated solution at 298 K. The inhibition ef-
ciency increases with the concentration of each inhibitor. As is
shown in Table 2, the inhibition efciency of EUI and CEPIP is
93.0% and 93.6% separately with the concentration 25 mg/L.
3.2. Potential polarization curves
Figs. 1 and 2 show the polarization curves of Q235 steel in salt-
water containing inhibitor EUI and CEPIP with various concentra-
Fig. 7. Inhibitors adsorbed on Fe surface in water solution.
Table 4
Interaction and binding energy of the two inhibitors on Fe (0 0 1) surface
Inhibitor EFe-inhibitor (kJ/mol) Ebinding (kJ/mol)
EUI 504.980 504.980
CEPIP 912.853 912.853
tion. It can be observed from Figs. 1 and 2 that anodic and
cathodic processes of Q235 steel corrosion in CO2 saturated solution
are suppressed evidently with both inhibitors and all their concen-
trations. However, when the concentration of EUI and CEPIP rises to
15 and 20 mg/L, the polarization degree do not change obviously.
Table 3 shows that the inhibition efciency of EUI and CEPIP is
93.4% and 94.7% separately with the concentration 25 mg/L.
3.3. Molecular dynamics simulation
The MD simulation is performed to study the adsorption behav-
ior of the two inhibitor molecules on the Fe (0 0 1) surface. The sys-
tem reaches equilibrium only if both of the temperature and
energy reach balance. Fig. 3(a) and (b) and Fig. 4(a) and (b) show
the temperature equilibrium curves and the energy uctuation
curves, respectively. It can be seen from Figs. 3 and 4 that the sys-
tem tends to equilibrium.
Figs. 5(a) and 6(a) show the initial conguration of EUI and CE-
PIP molecules, and Figs. 5(b) and 6(b) show the equilibrium cong-
uration of EUI and CEPIP molecules. Fig. 7 shows the system
simulated in water solution. The minimum distance between the
two inhibitor molecules and Fe surface is 0.131 and 0.146 nm,
respectively. According to the equilibrium conguration of the
two inhibitor adsorbed on Fe (0 0 1) surface, we can draw a conclu-
sion that both the two imidazoline derivatives can be absorbed on
the Fe surface through the imidazoline ring and heteroatoms, and
 S. Xia et al. / Corrosion Science 50 (2008) 20212029 2025

Fig. 8. Initial and equilibrium structure of EUI.

Fig. 9. Initial and equilibrium structure of CEPIP.

Table 5
Some bond length parameter of EUI and CEPIP

EUI bond Bond length (nm) CEPIP bond Bond length (nm)
Initial Equilibrium Initial Equilibrium
N1C2 0.1287 0.1433 N1C2 0.1257 0.1463
Table 6
N1C5 0.1471 0.1501 N1C5 0.1460 0.1497
Natural atomic charge
C2N3 0.1401 0.1398 C2N3 0.1568 0.1510
C2C6 0.1507 0.1600 C2C6 0.1501 0.1626 EUI atom Charge (C) CEPIP atom Charge (C)
N3C4 0.1469 0.1448 N3C4 0.1520 0.1554
Initial Equilibrium Initial Equilibrium
N3C7 0.1453 0.1454 N3C7 0.1541 0.1524
C4C5 0.1547 0.1506 N3C10 0.1517 0.1550 N1 0.2771 0.2279 N1 0.1703 0.1345
C7C8 0.1533 0.1550 C4C5 0.1537 0.1516 C2 0.1918 0.1499 C2 0.2246 0.1567
C8N9 0.1467 0.1452 C7C8 0.1534 0.1543 N3 0.2279 0.2364 N3 0.0431 0.0394
N1Fe 0.3335 C8N9 0.1460 0.1495 C4 0.0070 0.0108 C4 0.0049 0.0093
N3Fe 0.2985 C10C11 0.1528 0.1540 C5 0.0342 0.0533 C5 0.0419 0.0729
N9Fe 0.3112 C11C12 0.1537 0.1542 C6 0.1250 0.0989 C6 0.1406 0.0968
C11O16 0.1418 0.1481 C7 0.0004 0.0196 C7 0.0115 0.0136
C12O13 0.1437 0.1485 C8 0.0024 0.0118 C8 0.0087 0.0093
O13P14 0.1623 0.1630 N9 0.3949 0.4130 N9 0.3969 0.3790
P14O15 0.1605 0.1537 C10 0.0084 0.0145
P14O17 0.1480 0.1562 C11 0.0755 0.0804
P14O18 0.1607 0.1531 C12 0.0134 0.0158
N9Fe 0.31293 O13 0.3765 0.3761
O13Fe 0.30267 P14 1.2844 1.2935
P14Fe 0.29257 O15 0.4499 0.4617
O16Fe 0.27773 O16 0.3133 0.3069
O17Fe 0.29257 O17 0.5546 0.5119
O18Fe 0.26048 O18 0.4607 0.1139
2026 S. Xia et al. / Corrosion Science 50 (2008) 20212029

Table 7 3.4. Quantum chemistry calculation

Parameters of molecular properties

Parameter Initial Equilibrium 3.4.1. Equilibrium geometry structure

EUI We use Gaussian03 program DFT B3LLP method to fully opti-
E (eV) 21601.3699 21597.5195 mize geometrical structure of EUI and CEPIP. The optimized struc-
EHOMO (eV) 3.1894 2.5780 ture (initial) and absorbed equilibrium structure are shown in Figs.
ELUMO (eV) 3.7574 1.6071 8 and 9. Table 5 shows some optimized bond length parameter.
l (debye) 3.3134 2.3447
Edeform (kJ/mol) 371.562
It can be seen from Table 5 that, in the initial EUI molecule, the
bond length of N1C2 in the imidazoline ring is 0.1287 nm which
CEPIP
E (eV) 44362.1522 44355.2024
is longer than general CN double bond 0.1280 nm, while C2N3 is
EHOMO (eV) 5.9351 4.4287 0.1401 nm which is shorter than general CN single bond
ELUMO (eV) 2.4765 4.0640 0.1470 nm, the bond length have a tendency of averages which
l (debye) 12.0602 13.3385 indicates that there is a conjugation between C@N and N3. After
Edeform (kJ/mol) 670.406
adsorbed on the Fe surface, the bond length of N1C2 lengthens
to 0.1433 nm and C2N3 shortens to 0.1398 nm, the degree of con-
jugate action increases. The imidazoline ring is almost coplanar,
the alkyl chain approximately perpendicular to the surface. In this the dihedral angle of C5N1C2N3 and N1C2N3C4 change
way, the exposed part of Fe surface can be reduced by the covering from 0.262, 12.791 to 0.533, 7.477, respectively. The ethyl-
of the imidazoline ring and heteroatoms, consequently preventing amino is approximately parallel to the imidazoline ring and the
the surface from the water. Further more, as an unpolar tail the al- undecyl chain is more or less perpendicular to the ring. Compared
kyl chain prevents water molecules from contacting with the sur- to the initial structure, only the alkyl chain curls to some extent.
face. Therefore, the corrosion inhibition is achieved by the two In the initial CEPIP molecule, the bond length of N1C2 in the
factors. It can be inferred that the inhibitor molecules will form a imidazoline ring is 0.1257 nm which is shorter than general CN
water-proof lm on the Fe surface after being added to the double bond, while C2N3 is 0.1568 nm which is longer than gen-
solution. eral CN single bond. The conjugate action is weakened due to the
The value of the interaction and binding energy of the two following two reasons: on one hand, the import of 2,3-two hydro-
inhibitors on Fe (0 0 1) surface are listed in Table 4. It can be seen xyl propyl cation results in the occupation of the lone pair elec-
that both the binding energy were positive. The bigger the value trons on N3, therefore, no electron on N3 can delocalize to C=N;
of binding energy is, the more easier inhibitor adsorbs on the sur- on the other hand, there are two large substituents ethylamino
face, the higher the inhibitor efciency is. CEPIP has a greater bind- and 2,3-two hydroxyl propyl connected to the tetravalent nitrogen.
ing energy than that of EUI, therefore, it has a greater inhibitor Because of the steric hindrance, C2 gets away from N3 to N1. After
efciency, and this is consistent with experiment results. adsorbed on the Fe surface, the bond length of N1C2 lengthens to

Fig. 10. Initial geometry of EUI: (a) HOMO orbitals and (b) LUMO orbitals. Equilibrium geometry of EUI: (c) HOMO orbitals and (d)LUMO orbitals.
 S. Xia et al. / Corrosion Science 50 (2008) 20212029
0.1463 nm and C2N3 shortens to 0.1510 nm, which also have a
tendency of averages. However, the planar structure of imidazoline
is destroyed, the dihedral angle of C5N1C2N3 and N1C2N3
C4 change from 2.490, 18.029 to 2.681, 21.815, respectively.
No group is situated in the same plane with the imidazoline ring,
but the spatial orientations of the three group alkyl, ethylamino
and 2,3-two hydroxyl propyl is uniform. And the alkyl chain curls
too after absorbed on the surface.
After adsorbed on the Fe surface, some N and O atoms form sec-
ondary bonds with Fe atoms. The bond length is longer than strong
bond while shorter than sum of van der waals radii of atoms. The
van der waals radius of N and O atom is 0.335 and 0.334, respec-
tively, and the reasonable strong bond length to N and O atom is
0.235 and 0.234 [29].
3.4.2. Active sites
For the purpose of establishing the active site of the inhibitor
molecule, three inuence factors: natural atomic charge, distribu-
tion of frontier molecular orbital and Fukui indices are considered.
According to classical chemical theory, all chemical interactions
are by either electrostatic or orbital. Electrical charges in the mol-
ecule were obviously the driving force of electrostatic interactions.
It has been proven that local electron densities or charges are
important in many chemical reactions and physicochemical prop-
erties of compound [30]. Table 6 shows that N1, N3, C6, N9 carry
negative charges, C2 carries positive charge in EUI. This indicated
Fig. 11. Initial geometry of CEPIP: (a) HOMO orbitals and (b) LUMO orbitals. Equilibrium geometry of CEPIP: (c) HOMO orbitals and (d) LUMO orbitals.
2027
that N1, N3, C6, N9 are the negative charge centers which could of-
fer electrons to the Fe atoms to form coordinate bond; in CEPIP, all
O atoms and N1, C6, N9 carry larger negative charges, C2 and espe-
cially P14 carry positive charges. This indicated that all O atoms
and N1, C6, N9 are the negative charge centers which could offer
electrons to the Fe atoms to form coordinate bond, and P14 is
the positive charge center which can accept electrons from 3d orbi-
tal of the Fe atoms to form feedback bond, thus further strengthen-
ing the interaction of inhibitor and Fe surface. The parameters of
coordinate bond length are shown in Table 5.
According to the frontier molecular orbital theory (FMO) of
chemical reactivity, transition of electron is due to an interaction be-
tween HOMO (highest occupied molecular orbital) and LUMO (low-
est unoccupied molecular orbital) of reacting species. The energy of
HOMO is directly related to the ionization potential and character-
izes the susceptibility of the molecule toward attack by electro-
philes. Higher values of EHOMO are likely to indicate a tendency of
the molecule to donate electrons to appropriate acceptor molecules
with low energy or empty electron orbital. The energy of LUMO is di-
rectly related to the electron afnity and characterizes the suscepti-
bility of the molecule toward attack by nucleophiles. The lower the
values of ELUMO are, the stronger the electron accepting abilities of
the molecules are. It can be seen from Table 7 that comparing to
the initial structure, the values of EHOMO of the inhibitor increase
and ELUMO decrease, indicating that after adsorbed on the Fe surface,
the abilities of electron donating and accepting increase.
2028 S. Xia et al. / Corrosion Science 50 (2008) 20212029

Table 8 sion ability of inhibitor. Table 7 show the values of l and Edeform of
Fukui indices and components of molecular orbitals of EUI both the molecules are very great, especially CEPIP. It indicates that
Atom frE frN F Er FN
r HOMO (%) LUMO (%) both molecules are easier to be adsorbed at the Fe surface to pro-
Initial vide good inhibition ability.
N1 0.3251 0.4839 2.7739 3.5045 29.36 33.40 Figs. 10 and 11 show the HOMO and LUMO orbitals of the initial
C2 0.0351 0.6138 0.2995 4.4455 3.17 42.37 and equilibrium conguration of the two inhibitor molecules. The
N3 0.5320 0.1306 4.5390 0.9456 48.04 9.01 main components of molecular HOMO and LUMO orbitals are
C4 0.0113 0.0128 0.0967 0.0930 1.02 0.89
C5 0.0062 0.0050 0.0529 0.0363 0.56 0.35
listed in Tables 8 and 9. The sum of orbital coefcients square of
C6 0.0009 0.0084 0.0076 0.0607 0.08 0.58 participants (in percentage) represent their contribution to some
C7 0.0081 0.0145 0.0693 0.1051 0.73 1.00 molecular orbitals. In EUI, the HOMO is mainly constituted by
C8 0.0254 0.0033 0.2168 0.0238 2.30 0.23 N1, N3 and the LUMO is constituted by N1, C2, which indicating
N9 0.0334 0.0001 0.2850 0.0008 3.02 0.01
that N1, N3 can provide electrons and N1, C2 can accepting elec-
Equilibrium trons. The imidazoline ring can interact with Fe surface; in CEPIP,
N1 0.3429 0.4490 3.6194 7.6018 30.68 32.60
the HOMO is mainly constituted by O13, P14, O15, O17 and the
C2 0.0597 0.5260 0.6303 8.9062 5.34 38.19
N3 0.4364 0.1110 4.6061 1.8789 39.04 8.06 LUMO is constituted by N1, C2, which indicates that the phosphate
C4 0.0029 0.0131 0.0309 0.2211 0.26 0.95 group could provide electrons and imidazoline ring can accept
C5 0.0169 0.0196 0.1779 0.3322 1.51 1.42 electrons. CEPIP can interact with Fe surface through the imidazo-
C6 0.0038 0.1416 0.0398 2.3984 0.34 10.29 line ring and heteroatoms.
C7 0.0114 0.0047 0.1200 0.0795 1.02 0.34
Frontier orbital electron densities on atoms provide a useful
C8 0.0250 0.0027 0.2639 0.0449 2.24 0.19
N9 0.1031 0.0004 1.0884 0.0072 9.23 0.03 means for the detailed characterization of donoracceptor inter-
actions. In the case of a donor molecule, the HOMO density is
critical to the charge transfer (electrophilic electron density frE )
and in the case of an acceptor molecule, the LUMO density is
The total dipole moment l and deformability Edeform are param-
important (nucleophilic electron density frN ). However, frontier
eters characterizing the interaction between molecules. The defor-
electron densities can strictly be used only to describe the reac-
mability increases with the increase of l, making the molecule
tivity of different atoms in the same molecule [30]. To compare
easier to be adsorbed at the surface of iron. And the volume of mol-
the reactivities of different molecules, frontier electron densities
ecule increases with the increase of l, which increase the contact
have to be normalized by the energy of the corresponding fron-
area between molecule and surface of iron and increases the corro-
tier molecular orbitals: F Er frE =EHOMO ; F Nr frN =ELUMO . As is shown
in Tables 8 and 9, the active sites are in accord with the analysis
Table 9
above.
Fukui indices and components of molecular orbitals of CEPIP

Atom frE frN F Er FN

r HOMO (%) LUMO (%) 4. Conclusions
Initial
N1 0 0.5872 0.0001 6.4520 0 42.31 The molecular dynamics simulation results show that both the
C2 0 0.6016 0.0001 6.6010 0 43.35 two imidazoline derivatives can adsorb on the Fe surface through
N3 0.0002 0.0028 0.0011 0.0304 0.02 0.20 the imidazoline ring and heteroatoms with the alkyl chain approx-
C4 0 0.0106 0 0.1164 0 0.76
imately perpendicular to the surface. Quantum chemistry calcula-
C5 0 0.0019 0 0.0208 0 0.14
C6 0 0.0006 0 0.0068 0 0.04 tion results show that the imidazoline ring and heteroatoms are
C7 0 0.0332 0.0001 0.3650 0 2.39 the active sites of the two inhibitors. They can adsorb on Fe surface
C8 0 0.0005 0 0.0059 0 0.04 rmly by donating electrons to Fe atoms and accepting electrons
N9 0 0.0006 0 0.0061 0 0.04 from 3d orbitals of Fe atoms.
C10 0.0002 0.0132 -0.0008 0.1452 0.02 0.95
C11 0.0045 0.0028 0.0205 0.0303 0.43 0.20
C12 0.0012 0.0005 0.0056 0.0056 0.12 0.04 References
O13 0.0983 0.0004 0.4508 0.0043 9.54 0.03
P14 0.0322 0 0.1477 0.0003 3.13 0 [1] S.L. Li, Y.G. Wang, S.H. Chen, Some aspects of quantum chemical calculations
O15 0.1264 0 0.5794 0.0003 12.27 0 for the study of Schiff base corrosion inhibitors on copper in NaCl solutions,
O16 0.0077 0.0001 0.0351 0.0012 0.74 0.01 Corrosion Science 41 (1999) 17691782.
O17 0.7419 0 3.4014 0.0002 72.01 0 [2] G. Bereket, E. Hur, C. Ogretir, Quantum chemical studies on some imidazole
O18 0.0137 0 0.0626 0.0001 1.33 0 derivatives as corrosion inhibitors for iron in acidic medium, Journal of
Molecular Structure 578 (2002) 7988.
Equilibrium [3] N. Khalil, Quantum chemical approach of corrosion inhibition, Electrochimica
N1 0.0049 0.5580 0.0300 3.7363 0.46 43.39 Acta 48 (2003) 26352640.
C2 0.0040 0.4936 0.0247 3.3052 0.38 38.39 [4] L.M. Rodriguez-Valdez, A. Martinez-Villafane, D. Glossman-Mitnik,
N3 0.0002 0.0245 0.0013 0.1639 0.02 1.90 Computational simulation of the molecular structure and properties of
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