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Article

Application of DFT and TD-DFT on Langmuir Adsorption of Nitrogen and Sulfur Heterocycle Dopants on an Aluminum Surface Decorated with Magnesium and Silicon

by
Fatemeh Mollaamin
1,2,* and
Majid Monajjemi
3
1
Department of Food Engineering, Faculty of Engineering and Architecture, Kastamonu University, 37150 Kastamonu, Turkey
2
Department of Biology, Faculty of Science, Kastamonu University, 37150 Kastamonu, Turkey
3
Department of Chemical Engineering, Central Tehran Branch, Islamic Azad University, Tehran 1496969191, Iran
*
Author to whom correspondence should be addressed.
Computation 2023, 11(6), 108; https://doi.org/10.3390/computation11060108
Submission received: 24 March 2023 / Revised: 16 May 2023 / Accepted: 18 May 2023 / Published: 29 May 2023
(This article belongs to the Special Issue Density Functional Theory: Theory, Methods, Applications, and Recent Advances)
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Abstract

:
In this study, we investigated the abilities of nitrogen and sulfur heterocyclic carbenes of benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol regarding adsorption on an Al-Mg-Si alloy toward corrosion inhibition of the surface. Al-Si(14), Al-Si(19), and Al-Si(21) in the Al-Mg-Si alloy surface with the highest fluctuation in the shielding tensors of the “NMR” spectrum generated by intra-atomic interaction directed us to the most influence in the neighbor atoms generated by interatomic reactions of N → Al, O → Al, and S → Al through the coating and adsorbing process of Langmuir adsorption. The values of various thermodynamic properties and dipole moments of benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol adsorbed on the Al-Mg-Si increased by enhancing the molecular weight of these compounds as well as the charge distribution between organic compounds (electron donor) and the alloy surface (electron acceptor). Finally, this research can build up our knowledge of the electronic structure, relative stability, and surface bonding of various metal alloy surfaces, metal-doped alloy nanosheets, and other dependent mechanisms such as heterogeneous catalysis, friction lubrication, and biological systems.

1. Introduction

Among the various methods that minimize corrosion of metal surfaces, its inhibition by organic molecules is one of the most applicable methods because of its stability and low cost [1,2,3,4,5,6,7,8,9,10,11,12]. The existence of multiple bonds with π-electrons in these inhibitors help extensively in the formation of inactive blocks on metal surface and alloys, thereby closing the active sites of corrosion [13,14,15,16,17,18,19,20,21,22].
Based on some research, benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol are organic cyclic inhibitors for metal, semi-metal, or non-metal surfaces and their alloys by preventing undesirable surface reactions. It is obvious that a passive layer containing a complex between the surface and these inhibitors is generated when the surface is immersed in a solution consisting of benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol. The passive layer is insoluble in aqueous and many organic solutions. There is a positive connection between the thickness of the passive layer and the efficiency of preventing corrosion [23,24,25,26].
In the present work, we investigated adding some alloying elements of magnesium and silicon to an aluminum surface to form A-Mg-Si complex that was coated with organic compounds of benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol as the corrosion inhibitors of Al-Mg-Si alloy surface.

2. Theory, Materials, and Method

2.1. Heterocycle Inhibiting Agents

Recently, some researchers investigated how organic compounds can be employed as corrosion inhibitors for Al and its alloys because they consist of several heteroatoms (nitrogen, sulfur, oxygen, and phosphorus) that act as active adsorption centers. In this paper, we discuss the use of organic compounds of benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol as the corrosion inhibitors of an Al-Mg-Si alloy surface [27,28].
In this work, it was attributed to the inhibiting influence of the benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol on the adsorption of a stable complex on the aluminum alloy of the Al-Mg-Si surface.

2.2. Langmuir Adsorption Theory

The adsorption of benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol as corrosion inhibitors on the aluminum alloy surface of Al-Mg-Si in NaCl solution was performed [29,30,31] (Scheme 1).

2.3. Conceptual “ONOIM”

The three-layered pattern was applied for effective barriers of benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol adsorbing on an Al-Mg-Si alloy surface (Scheme 2) [32,33].
We found that the surface binding site preferences of the N-atom of benzotriazole, O-atom of 8-hydroxyquinoline, and S-atom of both 2-mercaptobenzothiazole and 3-amino-1,2,4-triazole-5-thiol on the adsorption site were largely affected by the presence of neighboring atoms (Scheme 2).
The average composition and crystal lattice parameters of Al-Mg-Si with a needle shape were considered based on Miller indices (including a = 6.75, b = 4.05, and c = 7.94 Å) [34,35,36].
The resulting observations showed that the Al-Mg-Si alloy surface calculated with the obtained structure properties was in good agreement with those metal alloys from other experimental computations [37,38,39,40,41,42].

2.4. DFT Calculations

The Al-Mg-Si alloy surface was built with a rigid system and a “Z-Matrix” format, for which a blank line was placed and after that, the following information has been illustrated. The rigid “PES” was performed with the “CAM-B3LYP” functional [43,44,45,46,47,48,49] while employing the “6-31+ G (d,p)/EPRIII/LANL2DZ” basis sets [50] for benzotriazole, 8-hydroxyquinoline, 2-mercaptobenzothiazole, and 3-amino-1,2,4-triazole-5-thiol adsorbing onto the Al-Mg-Si alloy surface using the “Gaussian 16” program package [35]. For the Al alloy surface, the small energy difference between the formations of adsorbate → Al-Mg-Si alloy complex could direct us to a somewhat coated surface for preventing the corrosion.

3. Results and Discussion

Many inhibitors reduce or prohibit the corrosion of aluminum via either cathode or anodic reactions. Usage of chromates (which extinguish the anodic reactions with coatings as the inhibitions for aluminum sheets) has been reduced because of toxicity. Other compounds such as phosphates, silicates, nitrates, nitrites, benzoates, and N-heterocyclic structures can influence the cathodic reactions in an aqueous environment.
In this study, the susceptibility of organic inhibitors (benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol), the characteristics of the aluminum alloy surface (Al-Mg-Si), and the adsorption conditions were considerable.

3.1. Infrared Spectroscopy Analysis

The infrared specifications around 1500–3500 cm−1 for benzotriazole → Al-Mg-Si, 2-mercaptobenzothiazole → Al-Mg-Si, 8-hydroxyquinoline → Al-Mg-Si, and 3-amino-1,2,4-triazole-5-thiol → Al-Mg-Si with the strongest peak at approximately 2700–2750 cm−1 are reported in Figure 1a–d.
The vibrational calculations were done for an aluminum alloy of Al-Mg-Si interacting with four organic inhibitors including benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol adsorbed onto this alloy surface, which produced the complexes of benzotriazole → Al-Mg-Si, 2-mercaptobenzothiazole → Al-Mg-Si, 8-hydroxyquinoline → Al-Mg-Si, and 3-amino-1,2,4-triazole-5-thiol → Al-Mg-Si (Table 1).
Table 1 shows physical and thermodynamic properties containing the dipole moment, thermal energy (∆E°), thermal enthalpy (∆H°), Gibbs free energy (∆G°), and entropy (S°). The values of various thermodynamic properties and dipole moments of benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol adsorbed on the Al-Mg-Si were enhanced by increasing the molecular weight of these compounds and the charge distribution between organic compounds (electron donor) and the surface (electron acceptor) (Table 1) [51].
As shown in Figure 2, ∆ G a d s o may depend on the interactions between the inhibiting agents and the Al alloy surfaces. In fact, a comparison to ∆ G a d s o was in good accordance with the calculated results and the validity of the picked isotherm for the adsorption procdure of benzotriazole → Al-Mg-Si, 2-mercaptobenzothiazole → Al-Mg-Si, 8-hydroxyquinoline → Al-Mg-Si, and 3-amino-1,2,4-triazole-5-thiol → Al-Mg-Si (Figure 2).
∆ G a d s o   amounts :   ∆ G a d s o = ∆ G i n h → [ A l − M g − S i ] o − ∆ G i n h o + ∆ G A l − M g − S i o .
On the basis of data in Table 1, we predicted that the adsorption of the inhibitor on the Al-Mg-Si alloy surface might be physical and chemical in nature. As shown in Figure 2, all the computed ∆ G a d s o amounts were very close, which exhibited the agreement of the evaluated data by all methods and the validity of the computations; this also represented the maximum fluctuation for benzotriazole → Al-Mg-Si, 2-mercaptobenzothiazole → Al-Mg-Si, 8-hydroxyquinoline → Al-Mg-Si, and 3-amino-1,2,4-triazole-5-thiol → Al-Mg-Si (Figure 2).

3.2. “NMR” Spectroscopy & “NBO” Analysis

The heterocyclic organic inhibitors of benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol showed an approximately identical behavior (20–200 ppm) for various atoms in the active sites of these compounds through the “NMR” properties and electrostatic potential “ESP” surface (Figure 3a–d,a’–d’). The strongest peak was seen at almost 20 ppm for these components. The weakest peaks appeared at 120–140 ppm for all four heterocyclic carbenes, which consisted of benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol (Figure 3a–d).
Langmuir adsorbing of benzotriazole → Al-Mg-Si, 2-mercaptobenzothiazole → Al-Mg-Si, 8-hydroxyquinoline → Al-Mg-Si, and 3-amino-1,2,4-triazole-5-thiol → Al-Mg-Si showed band wavelengths between 10 ppm and 1000 ppm, and the sharpest peaks were at about 10 ppm for these compounds (Figure 3a’–d’).
Then, the atomic charge and “NMR” data of the isotropic (σiso) and anisotropic shielding tensor (σaniso) for benzotriazole → Al-Mg-Si, 2-mercaptobenzothiazole → Al-Mg-Si, 8-hydroxyquinoline → Al-Mg-Si, and 3-amino-1,2,4-triazole-5-thiol → Al-Mg-Si were calculated using Gaussian 16 revision C.01 software [35]; the results are reported in Table 2 [52,53,54].
In addition, the NaCl solution influenced the electromagnetic traits of carbon, nitrogen, oxygen, sulfur, aluminum, magnesium, and silicon in benzotriazole → Al-Mg-Si, 2-mercaptobenzothiazole → Al-Mg-Si, 8-hydroxyquinoline → Al-Mg-Si, and 3-amino-1,2,4-triazole-5-thiol → Al-Mg-Si. Figure 4 indicates the isotropic (σCSI) and anisotropic (σCSA) chemical shielding tensors of some effective atoms on the adsorption sites of benzotriazole → Al-Mg-Si, 2-mercaptobenzothiazole → Al-Mg-Si, 8-hydroxyquinoline → Al-Mg-Si, and 3-amino-1,2,4-triazole-5-thiol → Al-Mg-Si (Table 2 and Figure 4).
Interatomic interactions, which are related positions of one, two, three, etc. atoms at a time, are written as a series expansion of functional parameters with interatomic potential [54].
Intra-atomic interactions consisted of Al-Al, Al-Mg, Al-Si, Mg-Mg, Mg-Si, and Si-Si; interatomic interactions were N → Al-Mg-Si, O → Al-Mg-Si, and S → Al-Mg-Si based on the of CAM-B3LYP/6-31+G(d,p)/EPR-III/LANL2DZ quantum mechanics calculations using the Gaussian 16 revision C.01 program (Figure 4).
In Figure 4, it can be observed that Al-Si(14), Al-Si(19), and Al-Si(21) directed us to the most influence in the neighbor atoms generated by interatomic reactions of N →Al, O → Al, and S → Al on the Al-Mg-Si alloy surface. Furthermore, the natural bond orbital (NBO) analysis of benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol adsorbed on the Al-Mg-Si surface is reported in Table 3.
In Table 3, the benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol adsorbed on the Al-Mg-Si indicate the electron donor atoms bonded to the aluminum atom as the electron acceptor on the alloy surface at the active site area. The bond orbitals of S7—Al14 in 3-amino-1,2,4-triazole-5-thiol → Al-Mg-Si, S10—Al17 in 2-mercaptobenzothiazole → Al-Mg-Si, O11—Al18 in 8-hydroxyquinoline → Al-Mg-Si, and N7—Al16 in Benzotriazole → Al-Mg-Si showed the maximum occupancy.

3.3. Nuclear Quadrupole Resonance (“NQR”)

The nuclear quadrupole resonance (NQR) frequency for benzotriazole → Al-Mg-Si, 2-mercaptobenzothiazole → Al-Mg-Si, 8-hydroxyquinoline → Al-Mg-Si, and 3-amino-1,2,4-triazole-5-thiol → Al-Mg-Si was measured (Table 4). There was an electric quadrupole moment that was accompanied by non-spherical nuclear charge distributions. So, the nuclear charge distribution deviated from that of a sphere as the oblate or prolate form of the nucleus [55,56,57,58]. In this research work, the electric potential was measured for benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol diffusing onto an Al-Mg-Si alloy surface (Table 4).
In addition, Figure 5a–d show the electric potential for elements of benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol that were adsorbed onto the Al-Mg-Si alloy.
Figure 5 shows the electric potential for carbon, nitrogen, oxygen, sulfur, aluminum, magnesium, and silicon in benzotriazole → Al-Mg-Si, 2-mercaptobenzothiazole → Al-Mg-Si, 8-hydroxyquinoline → Al-Mg-Si, and 3-amino-1,2,4-triazole-5-thiol → Al-Mg-Si.

3.4. Charge Density Analysis

By observing the intra/interatomic interactions between the organic inhibitor of benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol with the Al-Mg-Si alloy surface and the consequent formation of adsorbed surfaces of benzotriazole → Al-Mg-Si, 2-mercaptobenzothiazole→ Al-Mg-Si, 8-hydroxyquinoline → Al-Mg-Si, and 3-amino-1,2,4-triazole-5-thiol → Al-Mg-Si (Table 2), the charge density difference (“CDD”) for these structures at the adsorption site was estimated and plotted as shown in Figure 6.
Furthermore, the presence of covalent bonds in this alloy exhibited the identical energy value and outlook of the “PDOS” for the p orbitals of aluminum and silicon (Figure 7).
Furthermore, the Al-Mg-Si alloy surface showed an atomic charge (coulomb) of −1.200 before adsorption of heterocyclic carbenes and −1.41, −1.136, −1.230, and −0.407 after adsorption of benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol, respectively. Therefore, the charge densities for benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol on the Al-Mg-Si alloy surface were alternatively: ∆Q3-amino-1,2,4-triazole-5-thiol → Al-Mg-Si = 0.793 > ∆Q2-mercaptobenzothiazole → Al-Mg-Si = 0.064 > ∆Q8-hydroxyquinoline → Al-Mg-Si = −0.03 > ∆Qbenzotriazole → Al-Mg-Si = −0.21. The data explain the charge penetration through adsorption of benzotriazole on the Al-Mg-Si alloy surface.

3.5. Potential Energy of Interatomic Interactions

When binding occurred, we could observe the potential with both an attractive and a repulsive component [59]. Therefore, the optimized potential energies of the interatomic interaction for benzotriazole → Al-Mg-Si, 2-mercaptobenzothiazole → Al-Mg-Si, 8-hydroxyquinoline → Al-Mg-Si, and 3-amino-1,2,4-triazole-5-thiol → Al-Mg-Si were measured (Table 5).
Then, the distance between the nitrogen atom in benzotriazole, oxygen atom in 8-hydroxyquinoline, and sulfur atom in both 2-mercaptobenzothiazole and 3-amino-1,2,4-triazole-5-thiol with aluminum on the Al-Mg-Si nanosurface was evaluated (Table 5 and Figure 8).
Based on Figure 8, we assumed that for benzotriazole → Al-Mg-Si, 2-mercaptobenzothiazole → Al-Mg-Si, 8-hydroxyquinoline → Al-Mg-Si, and 3-amino-1,2,4-triazole-5-thiol → Al-Mg-Si, the Lennard-Jones potential as an intermolecular pair potential can be described [60,61].

3.6. “HOMO”, “LUMO”, and “UV-vis” Analysis

Ionization causes the highest occupied molecular orbital (“HOMO”) energy, and the electron affinity produces the lowest unoccupied molecular orbital (“LUMO”) energy, which were calculated and reported for benzotriazole → Al-Mg-Si, 2-mercaptobenzothiazole → Al-Mg-Si, 8-hydroxyquinoline → Al-Mg-Si, and 3-amino-1,2,4-triazole-5-thiol → Al-Mg-Si (Scheme 3). The “HOMO” (au), “LUMO” (au), and band energy gap “∆E = E LUMO- EHOMO” (ev) present a pictorial explanation of the frontier molecular orbitals and their respective positive and negative zones, which were important factors in identifying the molecular characteristics of effective compounds in these organic inhibitors (Scheme 3).
In fact, the compositions with a half-filled “HOMO-LUMO” band were not only metallic but could also turn to semiconducting, in which a molecular material is known to enter the zero-resistance state encountered for Al-Mg-Si toward adsorption of organic heterocyclic carbenes. The chemical reactivity of Al-Mg-Si was conducted by its low “HOMO–LUMO” gap, making it an appropriate electron acceptor. The energy gap between “HOMO” and “LUMO” distinguished the attributes of molecular electrical transport [62]. Based on the “Franck–Condon” principle, the maximum absorption peak (max) depends on a UV–visible spectrum of vertical excitation [63,64,65,66,67].
Finally, “TD-DFT/6-31+G (2d,p)/EPR-III/LANL2DZ” computation which has been a computational QM modelling methodology for studying the electronic structure of many-body systems [49,68,69,70,71,72], was done to identify the low-lying excited states of benzotriazole, 8-hydroxyquinoline, 2-mercaptobenzothiazole, and 3-amino-1,2,4-triazole-5-thiol adsorbing on the Al-Mg-Si alloy surface. The data contained the vertical excitation energies, oscillator strengths, and wavelengths, which are shown in Figure 9a–d.
As a matter of fact, based on the calculated values of the “UV-vis” spectra for benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol adsorbing onto the Al-Mg-Si alloy surface, there were maximum adsorption bands in the range of 1000–3000 nm wavelengths for these organic heterocyclic inhibitors of the joint metal alloy; these showed a sharp peak with an approximately 2000 nm wavelength (Figure 9a–d).

4. Conclusions

In this work, the adsorption and diffusion of benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol adsorbed onto an Al-Mg-Si alloy surface were studied based on the “Langmuir” theory using the “ONIOM” method with “high”, “medium”, and “low” levels of “EPR-III/6-31+G (d,p)/LANL2DZ” as well as semi-empirical and “MM2” basis sets using the program package “Gaussian 16” revision C.01.
In this research, the effectiveness of the (N- and S-) heterocycles as the Al alloy coating was investigated through the electromagnetic traits, a thermodynamic analysis, and characteristics of the environmental situation, which resulted in the complexes of benzotriazole → Al-Mg-Si, 2-mercaptobenzothiazole → Al-Mg-Si, 8-hydroxyquinoline → Al-Mg-Si, and 3-amino-1,2,4-triazole-5-thiol → Al-Mg-Si.
A special investigation of the mechanism of local minima in the adsorption potential energy insight denoted that the intact benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol were adsorbed with the aromatic ring parallel to the Al-Mg-Si alloy surface. In the favorite path, these (N- and S-) heterocycles remained parallel to the surface while running small single rotational steps with a “C–C” double-bond hinged top of a single Al element.

Author Contributions

F.M.: Conceptualization and idea, Methodology, Software, Validation, Formal analysis, Investigation, Data curation, Writing—original draft preparation, visualization, Supervision, Project administration. M.M.: Methodology, Software, Formal analysis, Investigation, Data curation, Writing—review and editing, Visualization, Resources. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Data Availability Statement

Not applicable.

Acknowledgments

In successfully completing this paper and its research, the authors are grateful to Kastamonu University for its support through the library, the laboratory, and scientific websites.

Conflicts of Interest

The authors declare no conflict of interest.

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Computation 11 00108 sch001a 550Computation 11 00108 sch001b 550
Scheme 1. Mechanism of Langmuir adsorption of the organic corrosion inhibitors of (a) benzotriazole, (b) 2-mercaptobenzothiazole, (c) 8-hydroxyquinoline, and (d) 3-amino-1,2,4-triazole-5-thiol on an Al-Mg-Si alloy surface.
Scheme 1. Mechanism of Langmuir adsorption of the organic corrosion inhibitors of (a) benzotriazole, (b) 2-mercaptobenzothiazole, (c) 8-hydroxyquinoline, and (d) 3-amino-1,2,4-triazole-5-thiol on an Al-Mg-Si alloy surface.
Computation 11 00108 sch001aComputation 11 00108 sch001b
Computation 11 00108 sch002 550
Scheme 2. The “ONIOM” layer of adsorption mechanism of N-heterocyclic carbene on an Al-Mg-Si alloy surface based on optimized coordination.
Scheme 2. The “ONIOM” layer of adsorption mechanism of N-heterocyclic carbene on an Al-Mg-Si alloy surface based on optimized coordination.
Computation 11 00108 sch002
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Figure 1. Infrared specifications for (a) benzotriazole → Al-Mg-Si, (b) 2-mercaptobenzothiazole → Al-Mg-Si, (c) 8-hydroxyquinoline → Al-Mg-Si, and (d) 3-amino-1,2,4-triazole-5-thiol → Al-Mg-Si using the “CAM-B3LYP” method with “6-31+ G (d,p)/EPRIII/LANL2DZ” basis sets. ε (M−1cm−1 or Lmol−1cm−1) is the absorbance unit and D (10−4 esu2 cm2) is the dipole strength via the esu or electrostatic unit, which is a unit of charge in the cgs (centimeter-gram-second) system.
Figure 1. Infrared specifications for (a) benzotriazole → Al-Mg-Si, (b) 2-mercaptobenzothiazole → Al-Mg-Si, (c) 8-hydroxyquinoline → Al-Mg-Si, and (d) 3-amino-1,2,4-triazole-5-thiol → Al-Mg-Si using the “CAM-B3LYP” method with “6-31+ G (d,p)/EPRIII/LANL2DZ” basis sets. ε (M−1cm−1 or Lmol−1cm−1) is the absorbance unit and D (10−4 esu2 cm2) is the dipole strength via the esu or electrostatic unit, which is a unit of charge in the cgs (centimeter-gram-second) system.
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Computation 11 00108 g002 550
Figure 2. Gibbs free energy of benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol as corrosion inhibitors on the Al-Mg-Si alloy surface in NaCl solution at 300 K.
Figure 2. Gibbs free energy of benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol as corrosion inhibitors on the Al-Mg-Si alloy surface in NaCl solution at 300 K.
Computation 11 00108 g002
Computation 11 00108 g003a 550Computation 11 00108 g003b 550
Figure 3. Chemical shift of “NMR” spectroscopy for (a) benzotriazole, (a’) benzotriazole → Al-Mg-Si, (b) 2-mercaptobenzothiazole, (b’) 2-mercaptobenzothiazole → Al-Mg-Si, (c) 8-hydroxyquinoline, (c’) 8-hydroxyquinoline → Al-Mg-Si, (d) 3-amino-1,2,4-triazole-5-thiol, and (d’) 3-amino-1,2,4-triazole-5-thiol → Al-Mg-Si indicating the active nitrogen, oxygen, and sulfur atoms in heterocyclic compounds approaching the nanosurface.
Figure 3. Chemical shift of “NMR” spectroscopy for (a) benzotriazole, (a’) benzotriazole → Al-Mg-Si, (b) 2-mercaptobenzothiazole, (b’) 2-mercaptobenzothiazole → Al-Mg-Si, (c) 8-hydroxyquinoline, (c’) 8-hydroxyquinoline → Al-Mg-Si, (d) 3-amino-1,2,4-triazole-5-thiol, and (d’) 3-amino-1,2,4-triazole-5-thiol → Al-Mg-Si indicating the active nitrogen, oxygen, and sulfur atoms in heterocyclic compounds approaching the nanosurface.
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Computation 11 00108 g004 550
Figure 4. Isotropic (σiso) and anisotropic (σaniso) shielding tensors through intra-atomic interactions with magnesium and silicon atoms on the alloy surface of Al-Mg-Si and interatomic interaction with organic inhibitors on the adsorption site of «N → Al, O → Al, S → Al».
Figure 4. Isotropic (σiso) and anisotropic (σaniso) shielding tensors through intra-atomic interactions with magnesium and silicon atoms on the alloy surface of Al-Mg-Si and interatomic interaction with organic inhibitors on the adsorption site of «N → Al, O → Al, S → Al».
Computation 11 00108 g004
Computation 11 00108 g005a 550Computation 11 00108 g005b 550
Figure 5. Electric potential for (a) benzotriazole, (b) 2-mercaptobenzothiazole, (c) 8-hydroxyquinoline, and (d) 3-amino-1,2,4-triazole-5-thiol adsorbed onto the Al-Mg-Si alloy.
Figure 5. Electric potential for (a) benzotriazole, (b) 2-mercaptobenzothiazole, (c) 8-hydroxyquinoline, and (d) 3-amino-1,2,4-triazole-5-thiol adsorbed onto the Al-Mg-Si alloy.
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Figure 6. Calculated electronic charge for aluminum atoms through intra-atomic interactions with magnesium and silicon on the alloy surface of Al-Mg-Si and through interatomic interactions with organic inhibitors on the adsorption site of «N → Al, O → Al, S → Al».
Figure 6. Calculated electronic charge for aluminum atoms through intra-atomic interactions with magnesium and silicon on the alloy surface of Al-Mg-Si and through interatomic interactions with organic inhibitors on the adsorption site of «N → Al, O → Al, S → Al».
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Figure 7. PDOS of Al-Mg-Si alloy surface with Fermi level = 0.
Figure 7. PDOS of Al-Mg-Si alloy surface with Fermi level = 0.
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Figure 8. Potential energy (kcal/mol) for benzotriazole, oxygen atom in 8-hydroxyquinoline, and sulfur atom in both 2-mercaptobenzothiazole and 3-amino-1,2,4-triazole-5-thiol with aluminum on the Al-Mg-Si nanosurface.
Figure 8. Potential energy (kcal/mol) for benzotriazole, oxygen atom in 8-hydroxyquinoline, and sulfur atom in both 2-mercaptobenzothiazole and 3-amino-1,2,4-triazole-5-thiol with aluminum on the Al-Mg-Si nanosurface.
Computation 11 00108 g008
Computation 11 00108 sch003a 550Computation 11 00108 sch003b 550
Scheme 3. The HOMO, LUMO, and band energy gap (ev) for three organic inhibitors for (a) benzotriazole → Al-Mg-Si, (b) 2-mercaptobenzothiazole, (c) 8-hydroxyquinoline, and (d) 3-amino-1,2,4-triazole-5-thiol → Al-Mg-Si.
Scheme 3. The HOMO, LUMO, and band energy gap (ev) for three organic inhibitors for (a) benzotriazole → Al-Mg-Si, (b) 2-mercaptobenzothiazole, (c) 8-hydroxyquinoline, and (d) 3-amino-1,2,4-triazole-5-thiol → Al-Mg-Si.
Computation 11 00108 sch003aComputation 11 00108 sch003b
Computation 11 00108 g009a 550Computation 11 00108 g009b 550
Figure 9. “UV-vis” spectra for (a) benzotriazole → Al-Mg-Si, (b) 2-mercaptobenzothiazole, (c) 8-hydroxyquinoline, and (d) 3-amino-1,2,4-triazole-5-thiol → Al-Mg-Si.
Figure 9. “UV-vis” spectra for (a) benzotriazole → Al-Mg-Si, (b) 2-mercaptobenzothiazole, (c) 8-hydroxyquinoline, and (d) 3-amino-1,2,4-triazole-5-thiol → Al-Mg-Si.
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Table
Table 1. Thermochemical traits for benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol as corrosion inhibitors on the aluminum alloy surface of Al-Mg-Si in NaCl solution at 300 K.
Table 1. Thermochemical traits for benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol as corrosion inhibitors on the aluminum alloy surface of Al-Mg-Si in NaCl solution at 300 K.
Compound∆H° × 10−4
(kcal/mol)		∆G° × 10−4
(kcal/mol)		S°
(cal/K·mol)		Dipole Moment
(Debye)
Al-Mg-Si−177.5928−177.595075.3211.7232
Benzotriazole−24.5172−24.519680.2553.3166
Benzotriazole →Al-Mg-Si−202.0579−202.060688.0855.7312
2-Mercaptobenzothiazole−69.5234−69.526085.6432.5108
2-Mercaptobenzothiazole → Al-Mg-Si−247.0475−247.050392.2323.3983
8-Hydroxyquinoline−29.5526−29.555183.3361.6389
8-Hydroxyquinoline → Al-Mg-Si−207.1047−207.107491.0092.7204
3-Amino-1,2,4-triazole-5-thiol −43.1336−43.135873.8391.5672
3-Amino-1,2,4-triazole-5-thiol → Al-Mg-Si−220.6678−220.670487.6572.4627
Table
Table 2. Atomic charge (Q) and NMR properties of some atoms of benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol in ppm adsorbed onto the Al-Mg-Si alloy surface.
Table 2. Atomic charge (Q) and NMR properties of some atoms of benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol in ppm adsorbed onto the Al-Mg-Si alloy surface.
Benzotriazole → Al-Mg-Si2-Mercaptobenzothiazole → Al-Mg-Si
Atom NumberσCSIσCSAQAtom NumberσCSIσCSAQ
C1120.1330144.3464−0.0637C1139.2936118.4161−0.0018
C2111.6339155.5331−0.0175C2134.3232132.1443−0.0112
C3131.8879138.77160.0136C3148.8807101.7628−0.2356
C4105.188360.85720.0406C4133.103092.28930.0725
C5127.8178132.38530.0024C5134.1798130.98000.0100
C6123.9381127.4240−0.0234C6132.5749132.8525−0.0102
N7−39.3745222.1133−0.247S7615.2211352.12800.4900
N813.1291127.7184−0.0999C866.1362138.3513−0.2058
N944.6789320.9807−0.1693N939.3993400.5662−0.284
Al10527.3315712.26200.0942S10354.0150388.31500.1054
Mg11769.6581592.78060.4635Al11228.95902775.11470.0704
Si12−608.09682457.1321−0.4390Mg12834.6620650.32780.4803
Mg13666.7797717.95990.7295Si13−457.25181719.0572−0.4733
Al14768.3930461.69280.1156Mg14626.04991179.76320.6134
Mg15816.8921478.51090.4296Al15488.41021924.50290.1084
Al161067.9909975.1162−0.3120Mg16756.9811356.88030.4321
Si17−488.22963646.7563−1.1411Al171074.22721028.1791−0.5734
Al181098.05532400.17350.2054Si18−335.56062228.3322−1.1356
Si19−518.58372423.5913−0.4705Al191000.86901408.42090.1846
Mg20519.2923858.56050.6638Si20−302.51801660.6930−0.4673
Al211167.00071138.12980.2251Mg21391.2234404.07770.6367
Al22838.89371929.86430.1949
8-Hydroxyquinoline → Al-Mg-Si3-Amino-1,2,4-triazole-5-thiol → Al-Mg-Si
Atom NumberσCSIσCSAQAtom NumberσCSIσCSAQ
C198.2089109.27730.0939N177.0484227.5978−0.3065
C2126.2638128.7805−0.0305C2109.273897.43580.2157
C3119.4349124.58880.0367C3117.4891102.62880.0089
C4126.8781157.6865−0.0100N4128.5710161.4324−0.0206
C5129.3314119.3934−0.0304N544.8980178.5759−0.2241
C6121.8894140.4467−0.0034N6277.728933.88100.0444
N7−1.6112512.5816−0.2439S7416.9395177.80800.2172
C8115.2833117.76500.0802Al8347.90271045.33110.0620
C9127.4460138.5220−0.0137Mg9764.3023425.99300.4335
C10121.2916130.89410.0016Si10300.1406902.6077−0.4546
O11108.4330157.2175−0.2988Mg11267.3292311.32490.6178
Al12249.78551244.52280.0838Al12316.71791168.72610.0707
Mg13805.0097564.92190.4314Mg13775.5928350.39790.3697
Si14−76.85441207.2367−0.4547Al141024.7125697.9996−0.4594
Mg15380.5230507.14330.6633Si15570.2486760.7295−1.2003
Al16260.06071196.87400.0732Al16814.3200922.16210.2166
Mg17802.8973597.25160.457Si17125.97421050.2575−0.4388
Al18915.6991955.5742−0.1330Mg18316.7269394.55250.6466
Si19375.35851390.2566−1.2295Al19737.75351175.39990.2012
Al20691.58781429.51380.2056
Si21−8.40491172.9932−0.5003
Mg22395.8393532.32530.6220
Al23729.90041438.67770.1992
Table
Table 3. NBO analysis of some atoms on the adsorption site for benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol bonded to the Al-Mg-Si alloy surface.
Table 3. NBO analysis of some atoms on the adsorption site for benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol bonded to the Al-Mg-Si alloy surface.
Heterocycles → Metal Alloy SurfaceBond OrbitalOccupancyHybrids
Benzotriazole → Al-Mg-SiBD (1) N7—Al161.594620.9033 (π) N + 0.4289 (sp2.20) Al
2-Mercaptobenzothiazole → Al-Mg-SiBD (1) S10—Al171.757370.7996 (π) S + 0.6006 (sp2.24) Al
8-Hydroxyquinoline → Al-Mg-SiBD (1) O11—Al181.620100.6467 (π) O + 0.7628 (sp2.07) Al
3-Amino-1,2,4-triazole-5-thiol → Al-Mg-SiBD (1) S7—Al141.774390.7708 (π) S + 0.6371 (sp2.56) Al
Table
Table 4. Electric potential for elements of benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol adsorbed on the Al-Mg-Si alloy surface according to a “CAM-B3LYP/EPR-III,6-31+G(d,p)” calculation extracted from the “NQR” method.
Table 4. Electric potential for elements of benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, and 3-amino-1,2,4-triazole-5-thiol adsorbed on the Al-Mg-Si alloy surface according to a “CAM-B3LYP/EPR-III,6-31+G(d,p)” calculation extracted from the “NQR” method.
Atom TypeBenzotriazoleAtom Type2-MercaptobenzothiazoleAtom Type8-HydroxyquinolineAtom Type3-Amino-1,2,4-triazole-5-thiol
C1−14.6152C1−14.5599C1−14.506N1−18.1871
C2−14.5807C2−14.5697C2−14.5761C2−14.4916
C3−14.5397C3−14.5643C3−14.5404C3−14.5524
C4−14.5511C4−14.5341C4−14.557N4−18.0542
C5−14.571C5−14.5706C5−14.5865N5−18.1750
C6−14.5828C6−14.5707C6−14.5682N6−18.0540
N7−18.1148S7−58.2774N7−18.1317S7−58.3546
N8−18.0989C8−14.5665C8−14.5394Al8−43.7470
N9−18.1089N9−18.1352C9−14.5679Mg9−38.70415
Al10−43.7244S10−58.445C10−14.5631Si10−48.3056
Mg11−38.7017Al11−43.7471O11−22.0527Mg11−38.9665
Si12−48.2798Mg12−38.6987Al12−43.7399Al12−43.7520
Mg13−38.9456Si13−48.3095Mg13−38.716Mg13−38.6765
Al14−43.7191Mg14−38.9819Si14−48.3057Al14−43.2490
Mg15−38.7164Al15−43.7426Mg15−38.9685Si15−48.0739
Al16−43.26Mg16−38.7278Al16−43.7423Al16−43.5918
Si17−48.0142Al17−43.2854Mg17−38.7179Si17−48.3095
Al18−43.595Si18−48.0619Al18−43.2654Mg18−38.975
Si19−48.2863Al19−43.6228Si19−48.0458Al19−43.6124
Mg20−38.9298Si20−48.3171Al20−43.602
Al21−43.6121Mg21−38.9744Si21−48.3141
Al22−43.623Mg22−38.9765
Al23−43.6074
Table
Table 5. Potential energy (kcal/mol) for benzotriazole, oxygen atom in 8-hydroxyquinoline, and sulfur atom in both 2-mercaptobenzothiazole and 3-amino-1,2,4-triazole-5-thiol with aluminum on the Al-Mg-Si nanosurface.
Table 5. Potential energy (kcal/mol) for benzotriazole, oxygen atom in 8-hydroxyquinoline, and sulfur atom in both 2-mercaptobenzothiazole and 3-amino-1,2,4-triazole-5-thiol with aluminum on the Al-Mg-Si nanosurface.
CompoundPotential Energy × 10−4
(kcal/mol)		Distance(Å)
Al-Mg-Si−177.5928--
Benzotriazole−24.5172--
Benzotriazole → Al-Mg-Si−202.0580N adsorbate → Al surface1.9518
2-Mercaptobenzothiazole−69.5235--
2-Mercaptobenzothiazole → Al-Mg-Si−247.0476S adsorbate → Al surface2.1998
8-Hydroxyquinoline−29.5527--
8-Hydroxyquinoline → Al-Mg-Si−207.1047O adsorbate → Al surface1.9098
3-Amino-1,2,4-triazole-5-thiol−43.1337--
3-Amino-1,2,4-triazole-5-thiol → Al-Mg-Si−220.6679S adsorbate → Al surface2.1998
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Mollaamin, F.; Monajjemi, M. Application of DFT and TD-DFT on Langmuir Adsorption of Nitrogen and Sulfur Heterocycle Dopants on an Aluminum Surface Decorated with Magnesium and Silicon. Computation 2023, 11, 108. https://doi.org/10.3390/computation11060108

AMA Style

Mollaamin F, Monajjemi M. Application of DFT and TD-DFT on Langmuir Adsorption of Nitrogen and Sulfur Heterocycle Dopants on an Aluminum Surface Decorated with Magnesium and Silicon. Computation. 2023; 11(6):108. https://doi.org/10.3390/computation11060108

Chicago/Turabian Style

Mollaamin, Fatemeh, and Majid Monajjemi. 2023. "Application of DFT and TD-DFT on Langmuir Adsorption of Nitrogen and Sulfur Heterocycle Dopants on an Aluminum Surface Decorated with Magnesium and Silicon" Computation 11, no. 6: 108. https://doi.org/10.3390/computation11060108

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