Copper Corrosion Protection by 4-Hydrocoumarin Derivatives: Insight from Density Functional Theory, Ab Initio, and Monte Carlo Simulation Studies

Saprizal Hadisaputra(1*), Agus Abhi Purwoko(2), Saprini Hamdiani(3)

(1) Chemistry Education Division, Faculty of Teacher Training and Education, University of Mataram, Jl. Majapahit No. 62, Mataram, 83125, Indonesia
(2) Chemistry Education Division, Faculty of Teacher Training and Education, University of Mataram, Jl. Majapahit No. 62, Mataram, 83125, Indonesia
(3) Department of Applied Chemistry, Chaoyang University of Technology, No. 168, Jifeng E. Rd., Wufeng District, Taichung 41349, Taiwan
(*) Corresponding Author


The corrosion inhibition performance of 4-hydrocoumarin derivatives has been studied using weight loss, electrochemical impedance spectroscopy, potentiodynamic polarization, and electrochemical frequency modulation techniques. However, experimental studies have not explained why the methoxy (OCH3) group contributes more to the increase in corrosion inhibition than the methyl (CH3) and chlorine (Cl) functional groups. In this theoretical study, the electronic aspect of the target corrosion inhibitors will be studied in detail to help strengthen the explanation in the experimental research. Density functional theory, ab initio, and Monte Carlo simulations have been used to analyze the corrosion inhibition performance of 4 curcumin derivatives against copper. The quantum chemistry approach is carried out under gas and aqueous conditions in neutral and protonated inhibitors. The Monte Carlo simulation was used to observe the dynamics and the mechanism of inhibition of the target molecule on the copper surface. The quantum chemistry approach can mimic the geometrical parameters of molecular inhibitors. It can also explain electronically why the OCH3 functional group is superior to other substituents. The adsorption energy of the 4-hydroquinone derivative is linearly correlated with the reported experimental study. The level of corrosion inhibition efficiency is OCH3 > CH3 > H > Cl.


copper; corrosion inhibitor; DFT; ab initio MP2; Monte Carlo; 4-hydrocoumarin

Full Text:

Full Text PDF


[1] Chaubey, N., Savita, S., Qurashi, A., Chauhan, D.S., and Quraishi, M.A., 2020, Frontiers and advances in green and sustainable inhibitors for corrosion applications: A critical review, J. Mol. Liq., 321, 114385.

[2] Hossain, N., Chowdhury, M.A., and Kchaou, M., 2021, An overview of green corrosion inhibitors for sustainable and environment friendly industrial development, J. Adhes. Sci. Technol., 35 (7), 673–690.

[3] Chauhan, D.S., Quraishi, M.A., and Qurashi, A., 2021, Recent trends in environmentally sustainable sweet corrosion inhibitors, J. Mol. Liq., 326, 115117.

[4] Verma, C., Ebenso, E.E., Quraishi, M.A., and Hussain, C.M., 2021, Recent developments in sustainable corrosion inhibitors: Design, performance and industrial scale applications, Mater. Adv., 2 (2), 3806–3850.

[5] Verma, C., Haque, J., Quraishi, M.A., and Ebenso, E.E., 2019, Aqueous phase environmental friendly organic corrosion inhibitors derived from one step multicomponent reactions: A review, J. Mol. Liq., 275, 18–40.

[6] Montemor, M.F., 2016, “Fostering green inhibitors for corrosion prevention” in Active Protective Coatings, Springer Series in Materials Science, vol 233, Eds. Hughes, A., Mol, J., Zheludkevich, M., and Buchheit, R., Springer, Dordrecht, 107–137.

[7] Umoren, S.A., Solomon, M.M., Madhankumar, A., and Obot, I.B., 2020, Exploration of natural polymers for use as green corrosion inhibitors for AZ31 magnesium alloy in saline environment, Carbohydr. Polym., 230, 115466.

[8] Dutta, A., Saha, S.K., Adhikari, U., Banerjee, P., and Sukul, D., 2017, Effect of substitution on corrosion inhibition properties of 2-(substituted phenyl) benzimidazole derivatives on mild steel in 1 M HCl solution: A combined experimental and theoretical approach, Corros. Sci., 123, 256–266.

[9] Berisha, A., 2022, An experimental and theoretical investigation of the efficacy of pantoprazole as a corrosion inhibitor for mild steel in an acidic medium, Electrochem, 3 (1), 28–41.

[10] Upadhyay, A., Purohit, A.K., Mahakur, G., Dash, S., and Kar, P.K., 2021, Verification of corrosion inhibition of mild steel by some 4-aminoantipyrine-based Schiff bases – Impact of adsorbate substituent and cross-conjugation, J. Mol. Liq., 333, 115960.

[11] Hadisaputra, S., Purwoko, A.A., Ilhamsyah, I., Hamdiani, S., Suhendra, D., Nuryono, N., and Bundjali, B., 2018, A combined experimental and theoretical study of (E)-ethyl 3-(4-methoxyphenyl) acrylate as corrosion inhibitor of iron in 1 M HCl solutions, Int. J. Corros. Scale Inhib., 7 (4), 633–647.

[12] Xu, S., Zhang, S., Guo, L., Feng, L., and Tan, B., 2019, Experimental and theoretical studies on the corrosion inhibition of carbon steel by two indazole derivatives in HCl medium, Materials, 12 (8), 1339.

[13] Zhao, W., Chang, T., Leygraf, C., and Johnson, C.M., 2021, Corrosion inhibition of copper with octadecylphosphonic acid (ODPA) in a simulated indoor atmospheric environment, Corros. Sci., 192, 109777.

[14] Tan, B., Zhang, S., Qiang, Y., Li, W., Liu, H., Xu, C., and Chen, S., 2019, Insight into the corrosion inhibition of copper in sulfuric acid via two environmentally friendly food spices: Combining experimental and theoretical methods, J. Mol. Liq., 286, 110891.

[15] Dahmani, K., Galai, M., Ouakki, M., Cherkaoui, M., Touir, R., Erkan, S., Kaya, S., and El Ibrahimi, B., 2021, Quantum chemical and molecular dynamic simulation studies for the identification of the extracted cinnamon essential oil constituent responsible for copper corrosion inhibition in acidified 3.0 wt% NaCl medium, Inorg. Chem. Commun., 124, 108409.

[16] Refait, P., Rahal, C., and Masmoudi, M., 2020, Corrosion inhibition of copper in 0.5 M NaCl solutions by aqueous and hydrolysis acid extracts of olive leaf, J. Electroanal. Chem., 859, 113834.

[17] Jmiai, A., Tara, A., El Issami, S., Hilali, M., Jbara, O., and Bazzi, L., 2021, A new trend in corrosion protection of copper in acidic medium by using Jujube shell extract as an effective green and environmentally safe corrosion inhibitor: Experimental, quantum chemistry approach and Monte Carlo simulation study, J. Mol. Liq., 322, 114509.

[18] Fouda, A.S., Rashwan, S.M., Kamel, M.M., and Khalifa, M.M., 2016, 4-Hydroxycoumarin derivatives as corrosion inhibitors for copper in nitric acid solutions, J. Mater. Environ. Sci., 7 (8), 2658–2678.

[19] Hajiahmadi, Z., and Tavangar, Z., 2019, Extensive theoretical study of corrosion inhibition efficiency of some pyrimidine derivatives on iron and the proposal of new inhibitor, J. Mol. Liq., 284, 225–231.

[20] Assad, H., and Kumar, A., 2021, Understanding functional group effect on corrosion inhibition efficiency of selected organic compounds, J. Mol. Liq., 344, 117755.

[21] Kumar, D., Jain, N., Jain, V., and Rai, B., 2020, Amino acids as copper corrosion inhibitors: A density functional theory approach, Appl. Surf. Sci., 514, 145905.

[22] Chiter, F., Costa, D., Maurice, V., and Marcus, P., 2021, DFT investigation of 2-mercaptobenzothiazole adsorption on model oxidized copper surfaces and relationship with corrosion inhibition, Appl. Surf. Sci., 537, 147802.

[23] Hadisaputra, S., Purwoko, A.A., Wajdi, F., Sumarlan, I., and Hamdiani, S., 2019, Theoretical study of the substituent effect on corrosion inhibition performance of benzimidazole and its derivatives, Int. J. Corros. Scale Inhib., 8 (3), 673–688.

[24] Behzadi, H., Roonasi, P., Momeni, M.J., Manzetti, S., Esrafili, M.D., Obot, I.B., Yousefvand, M., and Mousavi-Khoshdel, S.M., 2015, A DFT study of pyrazine derivatives and their Fe complexes in corrosion inhibition process, J. Mol. Struct., 1086, 64–72.

[25] Garcia-Ochoa, E., Guzmán-Jiménez, S.J., Hernández, J.G., Pandiyan, T., Vásquez-Pérez, J.M., and Cruz-Borbolla, J., 2016, Benzimidazole ligands in the corrosion inhibition for carbon steel in acid medium: DFT study of its interaction on Fe30 surface, J. Mol. Struct., 1119, 314–324.

[26] Costa, D., Ribeiro, T., Cornette, P., and Marcus, P., 2016, DFT modeling of corrosion inhibition by organic molecules: Carboxylates as inhibitors of aluminum corrosion, J. Phys. Chem. C, 120 (50), 28607–28616.

[27] Dao, D.Q., Hieu, T.D., Pham, T.L.M., Tuan, D., Nam, P.C., and Obot, I.B., 2017, DFT study of the interactions between thiophene-based corrosion inhibitors and an Fe4 cluster, J. Mol. Model., 23 (9), 260.

[28] Obot, I.B., Macdonald, D.D., and Gasem, Z.M., 2015, Density functional theory (DFT) as a powerful tool for designing new organic corrosion inhibitors. Part 1: An overview, Corros. Sci., 99, 1–30.

[29] Sengupta, S., Murmu, M., Murmu, N.C., and Banerjee, P., 2021, Adsorption of redox-active Schiff bases and corrosion inhibiting property for mild steel in 1 mol L−1 H2SO4: Experimental analysis supported by ab initio DFT, DFTB and molecular dynamics simulation approach, J. Mol. Liq., 326, 115215.

[30] Obot, I.B., Haruna, K., and Saleh, T.A., 2019, Atomistic simulation: A unique and powerful computational tool for corrosion inhibition research, Arabian J. Sci. Eng., 44 (1), 1–32.

[31] Zhu, Y., Sun, Q., Wang, Y., Tang, J., and Wang, Y., 2020, A study on inhibition performance of mercaptoalcohols as corrosion inhibitors by first principle and molecular dynamics simulation, Russ. J. Phys. Chem. A, 94 (9), 1877–1886.

[32] Kasprzhitskii, A., and Lazorenko, G., 2021, Corrosion inhibition properties of small peptides: DFT and Monte Carlo simulation studies, J. Mol. Liq., 331, 115782.

[33] Shamov, G.A., Schreckenbach, G., Martin, R.L., and Hay, P.J., 2008, Crown ether inclusion complexes of the early actinide elements, [AnO2(18-crown-6)]n+, An = U, Np, Pu and n= 1, 2: A relativistic density functional study, Inorg. Chem., 47 (5), 1465–1475.

[34] Pan, Q.J., and Schreckenbach, G., 2010, Binuclear hexa-and pentavalent uranium complexes with a polypyrrolic ligand: A density functional study of water-and hydronium-induced reactions, Inorg. Chem., 49 (14), 6509–6517.

[35] Fan, Y., Li, Y., Shu, X., Wu, R., Chen, S., Jin, Y., Xu, C., Chen, J., Huang, C., and Xia, C., 2021, Complexation and separation of trivalent actinides and lanthanides by a novel DGA derived from macrocyclic crown ether: Synthesis, extraction, and spectroscopic and density functional theory studies, ACS Omega, 6 (3), 2156–2166.

[36] Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Petersson, G.A., Nakatsuji, H., Li, X., Caricato, M., Marenich, A., Bloino, J., Janesko, B.G., Gomperts, R., Mennucci, B., Hratchian, H.P., Ortiz, J.V., Izmaylov, A.F., Sonnenberg, J.L., Williams-Young, D., Ding, F., Lipparini, F., Egidi, F., Goings, J., Peng, B., Petrone, A., Henderson, T., Ranasinghe, D., Zakrzewski, V.G., Gao, J., Rega, N., Zheng, G., Liang, W., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Throssell, K., Montgomery, Jr., J.A., Peralta, J.E., Ogliaro, F., Bearpark, M., Heyd, J.J., Brothers, E., Kudin, K.N., Staroverov, V.N., Keith, T., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A., Burant, J.C., Iyengar, S.S., Tomasi, J., Cossi, M., Millam, J.M., Klene, M., Adamo, C., Cammi, R., Ochterski, J.W., Martin, R.L., Morokuma, K., Farkas, O., Foresman, J.B., and Fox, D.J., 2016, Gaussian 09, Revision A.02, Gaussian, Inc., Wallingford CT.

[37] Islam, N., and Ghosh D.C., 2011, A new algorithm for the evaluation of the global hardness of polyatomic molecules, Mol. Phys., 109 (6), 917–931.

[38] Parr, R.G., Szentpaly, L.V., and Liu, S., 1999, Electrophilicity index, J. Am. Chem. Soc., 121 (9), 1922–1924.

[39] Yang, W., and Parr, R.G., 1985, Hardness, softness, and the Fukui function in the electronic theory of metals and catalysis, Proc. Natl. Acad. Sci. U. S. A., 82 (20), 6723–6726.

[40] Pearson, R.G., 1990, Hard and soft acids and bases—The evolution of a chemical concept, Coord. Chem. Rev., 100, 403–425.

[41] Pearson, R.G., 1988, Absolute electronegativity and hardness: Application to inorganic chemistry, Inorg. Chem., 27 (4), 734–740.

[42] Sastri, V.S., and Perumareddi, J.R., 1997, Molecular orbital theoretical studies of some organic corrosion inhibitors, Corrosion, 53 (8), 617–622.

[43] Guo, L., Safi, Z.S., Kaya, S., Shi, W., Tüzün, B., Altunay, N., and Kaya, C., 2018, Anticorrosive effects of some thiophene derivatives against the corrosion of iron: A computational study, Front. Chem., 6, 00155.

[44] Frenkel, D., and Smit, B., 2002, Understanding Molecular Simulations: From Algorithms to Applications, 2nd Ed., Academic Press, San Diego.

[45] Kirkpatrick, S., Gelatt, C.D., and Vecchi, M.P., 1983, Optimization by simulated annealing, Science, 220 (4598), 671–680.

[46] Hadisaputra, S., Purwoko, A.A., Savalas, L.R.T., Prasetyo, N., Yuanita, E., and Hamdiani, S., 2020, Quantum chemical and Monte Carlo simulation studies on inhibition performance of caffeine and its derivatives against corrosion of copper, Coatings, 10 (11), 1086.

[47] Stefanou, V., Matiadis, D., Melagraki, G., Afantitis, A., Athanasellis, G., Igglessi-Markopoulou, O., McKee, V., and Markopoulos, J., 2011, Functionalized 4-hydroxy coumarins: Novel synthesis, crystal structure and DFT calculations, Molecules, 16 (1), 384–402.

[48] Sagdinc, S., Kara, Y., and Kayadibi, F., 2014, Theoretical study of 11-thiocyanatoundecanoic acid phenylamide derivatives on corrosion inhibition efficiencies, Can. J. Chem., 92 (9), 876–887.

[49] Şahin, M., Gece, G., Karcı, F., and Bilgiç, S., 2008, Experimental and theoretical study of the effect of some heterocyclic compounds on the corrosion of low carbon steel in 3.5% NaCl medium, J. Appl. Electrochem., 38 (6), 809–815.

[50] Saranya, J., Sounthari, P., Parameswari, K., and Chitra, S., 2016, Acenaphtho[1,2-b]quinoxaline and acenaphtho[1,2-b]pyrazine as corrosion inhibitors for mild steel in acid medium, Measurement, 77, 175–186.

[51] Saha, S.K., Ghosh, P., Hens, A., Murmu, N.C., and Banerjee, P., 2015, Density functional theory and molecular dynamics simulation study on corrosion inhibition performance of mild steel by mercapto-quinoline Schiff base corrosion inhibitor, Phys. E, 66, 332–341.

[52] Tan, J., Guo, L., Wu, D., Wang, S., Yu, R., Zhang, F., and Kaya, S., 2020, Electrochemical and computational studies on the corrosion inhibition of mild steel by 1-hexadecyl-3-methylimidazolium bromide in HCl medium, Int. J. Electrochem. Sci., 15, 1893–1903.

[53] Huong, D.Q., Lan Huong, N.T., Anh Nguyet, T.T., Duong, T., Tuan, D., Thong, N.M., and Nam, P.C., 2020, Pivotal role of heteroatoms in improving the corrosion inhibition ability of thiourea derivatives, ACS Omega, 5 (42), 27655–27666.

[54] Chauhan, D.S., Verma, C., and Quraishi, M.A., 2021, Molecular structural aspects of organic corrosion inhibitors: Experimental and computational insights, J. Mol. Struct., 1227, 129374.


Article Metrics

Abstract views : 1845 | views : 850

Copyright (c) 2022 Indonesian Journal of Chemistry

Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.


Indonesian Journal of Chemistry (ISSN 1411-9420 / 2460-1578) - Chemistry Department, Universitas Gadjah Mada, Indonesia.

Analytics View The Statistics of Indones. J. Chem.