Corrosion Inhibition of Aluminium in Gas and Acid Media by Some Chalcone-Based N-(3-Aminopropyl)Imidazoles: TD-DFT-Based FMO, Conceptual DFT, QTAIM and EDA Studies

The efficacy and mode of action of five chalcone-based imidazole derivatives as corrosion inhibitors of aluminium metal in gas-phase and acidic medium have been investigated herein via quantum chemical calculations. Disper-sion-corrected DFT (DFT-D3) and time-dependent DFT (TD-DFT) calculations were performed at PBE0/def2-TZVP//PBEh-3c and CAM-B3LYP/def2-TZVP levels of theory, respectively. Conceptual DFT, the quantum theory of atoms-in-molecules (QTAIM) and local energy decomposition (LED) analyses have been performed. The LED analysis was performed at the coupled-cluster singles and doubles with perturbative triples (CCSD(T))/def2-SVP level of theory. Frontier molecular orbital energy gaps calculated using the TD-DFT method are found to lie in the range 3.574 - 4.444 eV, indicative of good adsorption and corrosion inhibition efficacies of the investigated molecules. The interactions between aluminium and the inhibitor molecules studied are found to be energetically favorable, owing to negative computed interaction energy values. Furthermore, QTAIM analysis revealed metal-carbon, met-al-oxygen


Introduction
In recent times, considerable research attention is focused on the design and synthesis of organic molecules as corrosion inhibitors for metals and their alloys.
Indeed, corrosion inhibition plays a crucial role in several industrial applications, since the deterioration of metals over time has a negative impact on their technical, economic, ecological and aesthetic quality standards [1]. It is well known that organic compounds containing heteroatoms (such as oxygen, nitrogen and sulfur) and conjugated double bonds are effective corrosion inhibitors [2]. Upon adsorption on a metal surface, electrons are transferred from an organic inhibitor to vacant orbitals of a metal, leading to covalent and/or non-covalent interactions (closed shell interactions) between the metal and the inhibitor. Based on several studies [3] [4] [5], it has been found that the adsorption of organic inhibitors on metal surfaces is mainly dependent on physicochemical properties of the inhibitors, including: the type of functional groups present, the electron density at the donor atoms (typically S, N and O), the molecular size, the mode of adsorption, the formation of organo-metal complexes, and the estimated area of the inhibitor on the metallic surface (degree of surface coverage). Furthermore, the need to choose corrosion inhibitors that are nontoxic and eco-friendly cannot be underestimated. In this regard, chalcones and their derivatives have drawn much interest, owing to their high tolerance in the human body (especially when complexed with metals) [6] [7]. Moreover, environmental pollution by inorganic corrosion inhibitors has prompted the search for green organic corrosion inhibitors that are biodegradable and do not contain heavy metals or other toxic constituents.
Aluminium is one of the most extensively used metals in the world today, but it undergoes deterioration when exposed to a corrosive environment (such as an acidic medium), in spite of its ability to form a thin protective oxide film on its surface. This has warranted the constant search for more effective and eco-friendly inhibitors of aluminium corrosion in a bid to increase the shelf life of aluminium-based materials [1].
Accordingly, the main objective of this work was to investigate the corrosion inhibitive capabilities, as well as the inhibitory modes of action, of some chal- It is interesting to note that theoretical methods such as those mentioned above have been successfully used in previous works to study the corrosion inhibition efficiency, molecular structures and electronic properties of organic corrosion inhibitors [8]- [14] for various metals, reason why such methods were employed in the present work. The DFT has been principally used in this study because many useful molecular parameters and descriptors in characterizing the corrosion inhibitor effectiveness on metal surfaces have been formulated within the framework of conceptual DFT [15].
To achieve the aforementioned objective of this work, the following five chalcone-based N-(3-aminopropyl)imidazoles have been studied (see

Computational Details and Theory
Theoretical calculations were carried out with the ORCA 4.1.0 and 4.2.0 computational packages [16]. The ORCA 4.2.0 package was only used for the calculations in solvent medium. The input files were prepared with the Avogadro 1.1.1 visualization software [17]. Geometry optimization and frequency calculations in both gas and solvent phases were carried out using the low-cost composite electronic structure approach dubbed PBEh-3c [18]. It is worth indicating that the PBEh-3c method is a highly efficient electronic structure approach for geometry optimization calculations and interaction energy computation for non-covalent complexes [18]. Here, the global hybrid variant of the Perdew-Burke-Ernzerhof (PBE) functional that incorporates a relatively large amount of non-local exact Hartree-Fock exchange (42%) is employed, along with a valence-double-zeta gaussian atomic orbital basis set (def2-mSVP) [18]. (1)- (6) and Equation (10): In Equations (1)-(4), µ and ( ) v r respectively represent the chemical and external potentials of an N-electron system with total energy E. IP and EA are the first vertical ionization potential and electronic affinity of the system, respectively. Values of IP and EA are calculated according to the following Equations (5) and (6).
where N E ,  with α = + or −, referring to nucleophilic or electrophilic respectively.
When two systems (for example a metal and an inhibitor) are brought together, electrons will flow from the system with lower electronegativity, χ (inhibitor) to that with higher χ (metal) until the chemical potentials become equal. In this work, the computed values of χ and η have been used to predict the fraction of the electron transferred (∆N) from the inhibitor to metallic surface as follows [28]: where metal inhibitor , χ χ and metal inhibitor , η η denote the absolute electronegativity and hardness of the species indicated as subscripts, respectively. The difference in electronegativity drives the electron transfer, and the sum of the hardness parameters acts as resistance [29]. In this study, Al 0 η = while the theoretical value of the work function of bulk aluminium, Al 4.28 eV φ = , were used in place of Al χ [30]. As such, Equation (10) can be rewritten thus: Another important parameter calculated in this study is the initial inhibitor-metal interaction energy ( ψ ∆ ), which has been introduced by Kokalj and Kovacevic [30]. The initial inhibitor-metal interaction energy ψ ∆ has been calculated as follows: which can equally be rewritten as follows: where metal inhibitor , χ χ and metal inhibitor , η η denote the absolute electronegativity and hardness of the species indicated as subscripts, respectively.
To calculate the proton affinity (PA) values of studied inhibitors, Equation (14) was employed: Solvent effects were invoked implicitly via the conductor-like polarizable continuum model (CPCM) [31] along with the Gaussian charge scheme and making use of scaled van der Waals solute cavity surfaces as implemented in the ORCA 4.2.0 program. Also, the Solvation Model Density (SMD) method was used in the accurate calculation of solvation free energies.

Frontier Molecular Orbitals (FMOs)
The FMOs (comprising the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO)) are the most important molecular orbitals used to study chemical trends. Although the commonly used Kohn-Sham DFT (KS-DFT) provides the best cost-accuracy ratio in the calculation of molecular orbital energies, it may fail to predict highly accurate molecular orbital energies [32]. This is particularly true for the LUMO eigenvalue and consequently the HOMO-LUMO gaps, reason being that KS-DFT is essentially a workhorse for ground state properties, by means of which the accurate computation of virtual LUMO orbitals is not guaranteed [32]. To circumvent this setback, the use of the time-dependent DFT (TD-DFT) method in conjunction with hybrid functionals to calculate more accurate LUMO eigenvalues (and subsequently more accurate HOMO-LUMO gaps) has been recommended [33]. Accordingly, the TD-DFT formalism has been used herein to compute accurate FMO energies and HOMO-LUMO gaps at the PBE0-D3/def2-TZVP//PBEh-3c level of theory. The PBE0 global hybrid functional has been employed here because it generally provides accurate estimates of the first excitation singles for systems with a predominance of local n → π* and π → π* transitions [34]. The FMO parameters of inhibitors calculated in this study include: the highest occupied molecular orbital energy (E HOMO ), the lowest unoccupied molecular orbital energy (E LUMO ), the energy gap ( Table 1. Based on the FMO theory, chemical reactivity is a function of the interaction between the HOMO and LUMO of the reacting species. E HOMO is usually linked to the capability of a chemical species to donate electron to neighboring molecules. Organic molecules with relatively less negative (or more positive) HOMO energy values are expected to have high electron donating abilities, leading to high corrosion inhibition efficiencies [5]. As can be observed from Table 1, the which reveals the predilection of HL3 to donate electrons to the incompletely filled 3p orbitals of the aluminium metal, as opposed to HL2 which has the least HOMO energy. It can equally be observed that the strongly deactivating nitro group in HL2 diminishes the electron donating ability of its HOMO, whereas the moderately activating alkoxy group in HL3 produces an opposite effect. Therefore, the adsorption of corrosion inhibitor molecules on the surface of aluminium could be improved upon by incorporating suitable functional site groups in the inhibitor. Unlike the trend shown by the HOMO energies, the LUMO energies on their part have revealed the ability of the LUMOs to accept electrons from the filled 3s orbital of aluminium, leading to a strong interaction energy. It is clear from Table 1 that HL2 with the lowest LUMO value will readily accept electrons from the filled 3s orbital of aluminium. It can equally be observed that HL3 bearing a moderately activating group is the least disposed to interact with the 3 s orbital of aluminium. The HOMO and LUMO isosurfaces of the inhibitors currently investigated are displayed in Table 2. As a general observation, the HOMO of each inhibitor molecule is largely localized around the imidazole moiety, which is indicative of the fact that the metal-HOMO interactions are mainly in the vicinity of the imidazole moiety. Contrary to the HOMOs, the LUMOs are almost entirely localized in the regions around the benzene ring (A) and the unsaturated keto-alkene moiety. On a relative scale, the HL2 inhibitor best interacts with the aluminium metal through its 3s orbital, given that E LUMO value is highest.
The energy gap (ΔE) is widely accepted as a measure of the global reactivity of a molecule. Generally, the inhibition efficiency of an organic inhibitor is expected to be high for a molecule with low ΔE [35]. From the values of ΔE, it is clear that the corrosion inhibition efficiency of the investigated inhibitors is ranked according to the order: HL2 > HL4 > HL3 > HL5 > HL1, which is quite consistent with the separate trends in both the HOMO and LUMO energies.

Reactivity Descriptors
The global reactivity parameters of the molecules studied: ionization energy (IP), electronic affinity (EA), global electronegativity (χ), global hardness (η), global softness (S), fraction of electrons transferred (ΔN), initial inhibitor-metal interaction energy (∆ψ), dipole moment, μ, total energy (TE) and electrophilicity index (ω), calculated based on the finite difference approximation, are listed in Table 3. The EA values show the following trend: HL4 < HL1 < HL5 < HL3 < HL2, which suggests that HL2 loses the highest amount of energy when the 3s orbital of the aluminium metal donates electrons to its LUMO, leading to a more stabilizing interaction between the metal and HL2 inhibitor. Indeed, the corrosion inhibition tendency shown by the EA parameter is in good agreement with that trend earlier revealed by the LUMO energies. This trend can be explained by the fact that the inhibitors with deactivating groups (except HL3), tend to resist electron donation compared to inhibitors with activating groups.   The influence of dipole moment on anticorrosion ability is controversial because some studies have shown that a small dipole moment is required for better inhibition, whereas others argue that a high value of the dipole moment enhances corrosion inhibition. The latter argument is based on the fact that the adsorption potency between the inhibitor and the metal surface increases with an increase in dipole moment [35].   This tendency decreases in the order: HL3 > HL4 > HL1 > HL2. It can also be noticed that the HL2 molecule has a ΔN value which is negative indicative of its very low partiality to offer electrons to the metal. Finally, the trend in the initial inhibitor-metal interaction energy (∆ψ) from Table 3 is as follows: HL4 > HL2 > HL3 > HL1 > HL5.

Study of One of the Most Feasible Inhibitor-Aluminium Interaction Patterns
As earlier mentioned, the formation of metallic complexes is one of the factors that affect the adsorption of an inhibitor onto the metal surface [3]. In a bid to simulate implicitly the interaction between inhibitor and metal, inhibitor-aluminium complexes were modelled and optimized without any constraints. Herein, the input chelates as shown in Figure 3 were modelled as a follow up of the bonding pattern proposed by Kalanithi and co-workers towards metal ions [39] and secondly, based on the HOMO isosurfaces localization pattern portrayed in Table 2, which shows the most plausible regions for the strongest metal-inhibitor interactions.   and HL5. This electron depletion tendency renders the aforementioned bonds slightly weaker.   Herein, the calculated binding energies (as indicated in Table 4) have been corrected for basis set superposition errors (BSSE) using the geometrical counterpoise correction (gCP) approach [19] Table 5. Large ρ(r) values and ∇ 2 ρ(r) < 0 indicate polar and non-polar covalent bonding interactions, whereas small ρ(r) values and ∇ 2 ρ(r) > 0 indicate closed-shell interactions [42]. Generally, ρ(r) is greater than 0.20 a.u. for covalent bonding interactions and less than 0.10 a.u. for closed-shell interactions [42]. The values of ∇ 2 ρ(r) and −G(r)/V(r) were also used to characterize the bonding interactions in the compounds studied. Generally, G(r) is the kinetic  energy density at the BCP (always positive) and V(r) is the potential energy density at the BCP (always negative) [43] When ∇ 2 ρ(r) > 0 and −G(r)/V(r) > 1, the interactions are noncovalent, whereas when ∇ 2 ρ(r) > 0 and 0.5 < −G(r)/V(r) < 1, the interactions are partially or partly covalent [44]. Based on the popular equation formulated by Espinosa [45] (E int = 0.5 V(r)), for estimating interatomic noncovalent bond interactions, selected bond interaction energies were calculated accordingly. A critical examination of Table 5 and Figure 5 shows that in addition to the Al-O (25) and Al-N (10) bonds earlier portrayed in the optimized complexes in

Local Energy Decomposition (LED) Analysis of the Inhibitor-Aluminium Complexes
In a bid to obtain more insight into the various types of contributions to the non-covalent interactions at the interface of the inhibitor fragment (fragment 1) and the aluminium atom fragment (fragment 2), the domain-based local pair natural orbital CCSD (T) method, i.e., DLPNO-CCSD (T), was used in calculating the interaction energy between the two fragments, albeit at a relative chemical accuracy. Decomposition of the interaction energy has been done via the local energy decomposition (LED) [22] scheme. In this study, the open-shell variant of the DLPNO-CCSD (T)/LED scheme [21] was employed. It should be recalled that the DLPNO-CCSD (T)/LED method takes into account counterpoise correction thus compensating for basis set incompleteness effects [22]. For exploratory and a more or less qualitative decomposition of the interaction energy, some chemically meaningful components of the interaction energy are presented in Table 6.
In Table 6 Table 6. Summary of some selected contributions (energies in Hatrees) of the LED at the DLPNO-CCSD (T) level of theory in gas phase. respect to the importance of dispersion. Hence, a ratio exceeding 1 unambiguously identifies a dispersion dominated interaction. Furthermore, a ratio between 0.5 and 1 points to an interaction with balanced contributions of dispersive and nondispersive characters, while a ratio smaller than 0.5 suggests an interaction somewhat dominated by nondispersive contributions [22]. It is evident from Table 6

Local Parameters of Studied Anticorrosion Inhibitors
In order to verify the probable role played by each atom in the molecules studied towards anticorrosion, their local reactivity parameters (Fukui functions (FF)) k f + and k f − , and local softness k s + and k s − based on Hirshfeld charges (Hirshfeld population analysis) have been calculated. It should be indicated that the Hirshfeld population scheme has been used here because it is not basis set dependent and give intuitively positive FF values [46]. However, due to orbital relaxation effects, some negative FF values can still be observed [47]. It is observed from Figure 6 that the sites acting favorably for nucleophilic attacks are

Molecular Properties of Protonated Inhibitors in Acidified Water
In acidic aqueous medium, corrosion inhibitors act as Lewis basis, as they accept The most favorable computationally tested protonation site which brought about the lowest molecular energy in all studied inhibitors was found to be at the 10N atom (see Figure 1) (after geometry optimization in water), corroborating the values of the condensed fukui functions for electrophilic attack ( k f − ) (see Figure 6) wherein one of the most favorable sites for electrophilic attacks is the 10 N atom. It is therefore evident that in acidic aqueous medium, the 10 N atom will be unavailable for any substantial interaction with the aluminium surface.
According to proton affinity values of the studied inhibitors calculated at the PBEh-3c level of theory, the inhibition efficiency ranking for studied inhibitors is: HL3 > HL5 > HL4 > HL1 > HL2. This trend can be explained from the fact that the electron depleting groups tend to reduce the proton affinities while donor groups improve on the proton affinity power of the studied molecules. Interestingly, Figure 7 reveals the fact that the PAs (inhibition efficacy in acid medium) of the HL1 and HL3 are found to be directly proportional to temperature, within the studied temperature range 273.15 -343.15 K, whereas the HL2, HL4 and HL5 inhibitors show proton affinities that are inversely proportional to temperature within the studied temperature range, albeit with very slight changes in PAs. Consequently, at relatively higher temperatures in aqueous medium, the HL1 and HL3 are found to be more effective anticorrosion inhibitors  than at lower temperatures, in contrast to the HL2, HL4 and HL5 compounds that will be better corrosion inhibitors at relatively higher temperatures.
Given that the energy gap in the protonated species is lower than unprotonated species in gas phase (see Table 1 and Table 6), it is can be predicted that the atoms of the imidazole moiety and the 9C, 8C, 7C and 6C of the chalcone moiety will be involved in the interaction with the aluminium surface. This improved interaction is confirmed by the slight increase in planarity of the 9C-8C-7C-6C moiety of the protonated molecules.
The calculated dihedral angle φ (9C-8C-7C-6C) in H 2 L1 + is found to be 179.3˚ whereas in the HL1 molecule it is 178.9˚. It must be stressed that high degree of planarity, that may lead to a high electronic delocalization are typical of a resonant system [37]. This indicates that the molecular interaction with the metallic surface can also occur through the π orbitals of the chalconic moiety in aqueous phase. The same observation is obtained for H 2 L5 + and its HL5 counterpart wherein the φ (9C-8C-7C-6C) dihedral angle is respectively 179.7˚ and 179.1˚.
However, the planarity of the 9C-8C-7C-6C portion of the H 2 L4 + molecule is found to lower compared to the HL4 counterpart. The dihedral angles φ (9C-8C-7C-6C) here are found to be 179.3˚ and 179.7˚, showing that the interaction of this portion of the molecule with the aluminium surface drops upon protonation in acidic aqueous medium. In acidic aqueous medium also, studies have shown that the energy gaps of the protonated species presented in Table 7 witness a decrease compared to the values in the unprotonated species in the gas phase reminiscence of an even improved adsorption in acidic aqueous medium of the unprotonated species in gas phase.

Aqueous Absolute Standard One-Electron Redox Potentials of Studied Inhibitors (Inhs)
In a bid to gain more knowledge on how well the inhibitors (Inh s = HL1, HL2, HL3, HL4 and HL5) under study bequeath electrons in aqueous solution phase, their one-electron redox process was investigated according to Scheme 1, and were used to determine their standard absolute redox potentials (°c alc E ) accordingly.
Herein, the absolute redox potentials have been computed from the Gibbs free energy associated with the oxidation-reduction process of the inhibitors in aqueous solution phase, by considering Equation (19) It should be noted that, the free energy of the electron is not taken into account since the addition of another half-cell reaction for the reference electrode automatically cancels the energy of the electron out. It could also be argued that the ionic convention of an electron leads to a zero value of its free energy in the gas and solution phase, hence it is typically ignored [48].
In the ORCA program, the term ENP G ∆ represents the bulk electrostatic contribution arising from the interaction of the medium and the molecular surface charges while the cavity-dispersion solvent-structure term ( CDS G ∆ ) represents the free energy change associated with the solute-solvent interactions in the first solvation shell [50]. The term From Table 8, it can be noticed that the electron withdrawing groups show higher redox potentials which thus diminishes their affinity for aluminium in aqueous solution, which can influence their chelating ability for aluminium.
Accordingly, the absolute redox potential ranking is as follows: HL2 > HL4 > HL5 > HL1 > HL3. It is thus expected that the HL3 will bequeath electrons in aqueous solution phase most easily, corroborating finding made on their E HOMO studies which reveals the predilection of HL3 to donate electrons most. As expected, the HL2 redox couple has the least negative absolute redox potential suggestive of its resistance to bequeath electrons easily in aqueous medium. As already mentioned, the electron withdrawing/electron donating effect should be highly relevant for donor-acceptor interactions in the resulting inhibitor-aluminium complexes, since these are typically electrostatic in nature.

Conclusion
Quantum chemical calculations have been undertaken to evaluate the anticorrosion efficacy and modes of action of five chalcone-based imidazole ligands on aluminium in both gas phase and acidic aqueous medium. Computed values of the frontier molecular energy gaps in gas phase are in the range 3.574 eV and 4.444 eV, which are found to be lower than similar values in the literature, suggestive of very good adsorptive and inhibition capacity [5]. In order to model the inhibitor-aluminium interaction patterns, the geometries of inhibitor-aluminium complexes were fully optimized. All calculated interaction energies and Gibbs free energies at 298.15 K and 1.00 atm, were found to be negative, which shows that the formation of the investigated inhibitor-aluminium complexes is energetically favorable. QTAIM analysis on these complexes in gas phase further re-