Theoretical Investigation of Corrosion Behaviors of Pyridazine Derivatives Using DFT Calculations

Öz

Metal corrosion represents a significant challenge in industrial applications, leading to substantial economic losses and safety concerns. In this study, the corrosion inhibition performance of selected pyridazine derivatives was systematically investigated using density functional theory (DFT). Quantum chemical calculations were performed at the B3LYP/6-311G(d,p) level to evaluate frontier molecular orbitals (EHOMO, ELUMO), energy gap (ΔE), and global reactivity descriptors including electronegativity (χ), hardness (η), softness (S), electrophilicity index (ω), and fraction of electron transfer (ΔN). The results reveal a clear structure–reactivity relationship, where molecules with higher electron-donating ability and lower energy gaps exhibit enhanced inhibition performance. Among the studied compounds, compound 5 showed the highest inhibition potential due to its lowest ΔE and highest ΔN values. Molecular electrostatic potential (MEP) and density of states (DOS) analyses further support strong adsorption tendencies. The findings provide a comprehensive theoretical framework for understanding corrosion inhibition mechanisms of pyridazine derivatives and contribute to the rational design of efficient organic inhibitors. These findings provide useful theoretical support for corrosion inhibition applications in acidic media.

Anahtar Kelimeler

• Pyridazine derivatives
• corrosion inhibition
• density functional theory
• quantum chemical descriptors
• MEP
• DOS

Kaynakça

1. 1. Ashassi-Sorkhabi H, Seifzadeh D. The inhibition of steel corrosion in hydrochloric acid solution by juice of prunus cerasus. Int J Electrochemical Sci. 2006;1(2):92-98.
2. 2. Behpour M, Ghoreishi SM, Soltani N, et al. The inhibitive effect of some bis-N,S-bidentate Schiff bases on corrosion behavior of mild steel in HCl solution. Corros Sci. 2009;51:1073-1082.
3. 3. Lukovits I, Kálmán E, Zucchi F. Corrosion inhibitors—Correlation between electronic structure and efficiency. Corros Sci. 2001;57:3-8.
4. 4. Khaled KF. Molecular simulation, quantum chemical calculations and electrochemical studies for inhibition of mild steel by triazoles. Electrochim Acta. 2008;53(9):3484-3492.
5. 5. Ogede RO, Abdulrahman NA, Apata DA. DFT computational study of pyridazine derivatives as corrosion inhibitors for mild steel in acidic media. GSC Advan Res Rev. 2022;11(03):106-114.
6. 6. Mrani SA, Ech-Chihbi E, Salim R, et al. Experimental, theoretical and MC simulation investigations of the inhibitory efficiency of novel non-toxic pyridazine derivatives inhibition on carbon steel in 1 M HCl solution. J Mol Liq. 2023;382(3):122043.
7. 7. Kaya S, Putz MV. Atoms-In-Molecules’ Faces of Chemical Hardness by Conceptual Density Functional Theory. Molecules. 2022;27(24):8825.
8. 8. Verma C, Chauhan DS, Aslam R, et al. Principles and theories of green chemistry for corrosion science and engineering: design and application. Green Chem. 2024;26:4270-4357. 9. Ebenso EE, Isabirye DA, Eddy NO. Adsorption and quantum chemical studies on the inhibition potentials of some thiosemicarbazides for the corrosion of mild steel in acidic medium. Int J Mol Sci. 2010;11:2473-2498.

9. 10. Akbas E, Akbas BC. Investigation of the adsorption of dacarbazine (DTIC), which is used as an anticancer drug, on graphene oxide by DFT calculation method. Int J Chem Technol. 2023;7(2):197-203.
10. 11. Akbas E. DFT investigation of adsorption of pyrimidine derivatives on graphene oxide. J Ata-Chem. 2023;3(2):32-38. 12. Karakuş N and Kaya S. A Density Functional Theory (DFT) based Analysis on the Inhibition Performances of Some Triazole Derivatives for Iron Corrosion. Cumhuriyet Sci J. 2023;44(3):491–496.
11. 13. Quadri TW, Akpan ED, Elugoke SE, et al. A critical review of coordination chemistry of pyrimidine and pyridazine compounds: Bonding, chelation and corrosion inhibition. Coordination Chemistry Reviews. 2025;523:216-285.
12. 14. Obot IB, Macdonald DD, Gasem ZM. Density functional theory (DFT) as a powerful tool for designing new organic corrosion inhibitors. Part 1: An overview. Corros Scie. 2015;99:1-30.
13. 15. Putz MV. Electronegativity and chemical hardness: Different patterns in quantum chemistry. Curr Phy Chem. 2011;1(2):111-139.
14. 16. Obot, IB, Onyeachu IB, Kaya S. Chapter 3 - Density Functional Theory: Practical Application and Their Limitations in Corrosion Inhibition Research. Interdiscip Res Center Adv Mat. 2023.
15. 17. Kaya S, Siddique F, Isin DO, et al. Inhibition performances of new pyrazole derivatives against the corrosion of C38 steel in acidic medium: Computational study. Results in Surfaces and Interfaces. 2024;14(1):100184.
16. 18. Kumari D, Sharma P, Tukur B, et al. Revealing the effects of pressure on periodic descriptors. Mol Phy. 2025;123(4):e2385599.
17. 19. Okay M, Ergan E, Akbaş BÇ, et al. Determination of electronic characteristics of tetrahydro pyrimidine derivatives and investigation of usability as anti-corrosion. Intern J Chem Techn. 2021;5(1):59-66.
18. 20. Frisch MJ, Trucks GW, Schlegel HB, et al. Gaussian 16, Revision C.01. Gaussian, Inc., Wallingford CT; 2016. 21. Becke AD. Density-functional thermochemistry. II. The effect of the Perdew–Wang generalized-gradient correlation correction. J. Chem. Phys. 1992;97(12):9173-9177.
19. 22. Koopmans T. Über die Zuordnung von Wellenfunktionen und Eigenwerten zu den einzelnen Elektronen eines Atoms. Physica. 1934;1(1-6):104-113.
20. 23. Geerlings P, Proft FD, Langenaeker W. Conceptual density functional theory. Chem Rev. 2003;103(5):1793-1873.
21. 24. Senet P. Chemical hardnesses of atoms and molecules from frontier orbitals. Chem Phy. Lett. 1997;275:527-532.
22. 25. Pauling L. The Nature of the Chemical Bond . Cornell University Press, Ithaca, New York; 1960. 26. Parr RG, Donnelly RA, Levy M, et al. Electronegativity: The density functional viewpoint. J Chem Phy. 1978;68:3801-3807.
23. 27. Parr RG, Szentpaly L, Liu S. Electrophilicity Index. J Am Chem Soc. 1999;121:1922-1924.
24. 28. Sastri VS, Perumareddi JR. Molecular Orbital Theoretical Studies of Some Organic Corrosion Inhibitors. Corros Sci. 1997;53(8):617-622.
25. 29. Gomez B, Likhanova NV, Dominguez-Aguilar MA, et al. Quantum Chemical Study of the Inhibitive Properties of 2-Pyridyl-Azoles. J Phy Chem B. 2006;110(18):8928-8934.
26. 30. Gupta RK, Malviya M, Verma C, et al. Aminoazobenzene and diaminoazobenzene functionalized graphene oxides as novel class of corrosion inhibitors for mild steel: Experimental and DFT studies. Mater Chem Phys. 2017;198:360-373.
27. 31. Gece G. The use of quantum chemical methods in corrosion inhibition studies: A review. Corros Sci. 2008;50(11):2981-2992.
28. 32. Beniken M, Daoui S, Alaoui Mrani S, et al. Electrochemistry evaluation and quantum corroboration with surface analysis of potential anticorrosive of two new pyridazine derivatives for mild steel in 1 M HCl solution. Colloids and Surfaces A: Physicochem and Engin Asp. 2023;673:131699.
29. 33. Quadri TW, Olasunkanmi LO, Akpan ED, et al. Development of QSAR-based (MLR/ANN) predictive models for effective design of pyridazine corrosion inhibitors. Materialstoday Comm. 2022;30:103163.
30. 34. Gece G, Bilgiç S. A theoretical study of some hydroxamic acids as corrosion inhibitors for carbon steel. Corros Sci. 2010;52(10):3304–3308.
31. 35. Udhayakalaa P, Rajendiranb TV, Gunasekaranc S. A theoretical study of some barbiturates as corrosion inhibitors for mild steel. J Cheml Pharm Res. 2014;6(4):1027-1039.
32. 36. Hsissou R, Benhiba F, Abbout S, et al. Trifunctional epoxy polymer as corrosion inhibition material for carbon steel in 1.0 M HCl: MD simulations, DFT and complexation computations. Inor Chem Comm. 2020;115:107858.
33. 37. Benmahammed I, Douadi T, Issaadi S, et al. Electrochemical, DFT and md simulation investigations of the corrosion inhibition properties of heterocyclic sulfide derivatives for mild steel in acidic medium. Surface Rev and Lett. 2020;27(6):1950165.
34. 38. O’Boyle NM, Tenderholt AL, Langner KM. CCLIB: A library for package-independent computational chemistry algorithms. J Comput Chem. 2008;29:839-845.