Multiscale Computational Study of Corrosion Inhibition Mechanism for Five Cyclic Amino Acids Based on Density Functional Theory (DFT) and Molecular Dynamics (MD) Simulations

doi:10.11902/1005.4537.2025.098

Journal of Chinese Society for Corrosion and protection

2026, Vol. 46

Issue (1): 261-272 DOI: 10.11902/1005.4537.2025.098

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Multiscale Computational Study of Corrosion Inhibition Mechanism for Five Cyclic Amino Acids Based on Density Functional Theory (DFT) and Molecular Dynamics (MD) Simulations

BAI Ruiyu¹, HUANG Wei'an¹^,²(

), JIA Jianghong³, ZHANG Yanming⁴, LIU Yunfeng⁵, WANG Zengbao¹

^1.School of Petroleum Engineering, China University of Petroleum (East China), Qingdao 266580, China
^2.National Key Laboratory of Deep Oil and Gas, China University of Petroleum (East China), Qingdao 266580, China
^3.Sinopec, Zhongyuan Oilfield Company, Engineering Technology Management Department, Puyang 457001, China
^4.Petro China Changqing Oilfield Company Oil and Gas Process Research Institute, Xi'an 710018, China
^5.Petro China Southwest Oil & Gasfield Company, Research Institute of Natural Gas Technology, Chengdu 610213, China

Cite this article:

BAI Ruiyu, HUANG Wei'an, JIA Jianghong, ZHANG Yanming, LIU Yunfeng, WANG Zengbao. Multiscale Computational Study of Corrosion Inhibition Mechanism for Five Cyclic Amino Acids Based on Density Functional Theory (DFT) and Molecular Dynamics (MD) Simulations. Journal of Chinese Society for Corrosion and protection, 2026, 46(1): 261-272.

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Abstract

The corrosion inhibition performance and mechanisms of five cyclic amino acids, namely tryptophan, histidine, proline, phenylalanine, and tyrosine, for Fe in HCl solution were investigated by means of molecular dynamics (MD) simulations and density functional theory (DFT) calculations. The results demonstrate that all the five cyclic amino acids exhibit significant corrosion inhibition effect. Among others, tryptophan (Trp) exhibits the most outstanding inhibition performance, which may be attributed to the unique π-electron conjugation effect of its indole ring and the strong coordinating ability of its amino group. MD simulations reveal that Trp forms a dense adsorption film on the metal surface, with a significantly higher adsorption energy (-381.45 kJ/mol) rather than other amino acids (e.g., histidine: -307.11 kJ/mol). Its molecular orientation facilitates the construction of a hydrophobic barrier, effectively impeding the ingress of H⁺/Cl^- ions. DFT analysis further elucidates that the highest occupied molecular orbital (HOMO) of Trp is localized on the indole ring and amino group, enabling strong chemical bonding with vacant d-orbitals of metal Fe via electron back-donation. Conversely, the lowest unoccupied molecular orbital (LUMO) is distributed over the indole ring and carboxyl group, enhancing its adsorption stability. Trp's global reactivity parameter (ΔN = 0.456) is considerably higher than that of other amino acids (e.g., proline ΔN = 0.325), indicating superior charge transfer capability. This results in a pronounced synergistic effect suppressing both anodic metal dissolution and cathodic hydrogen evolution. Consistent with the theoretical findings, electrochemical evaluation confirms that Trp also delivers the best corrosion inhibition performance.

Key words: cyclic amino acid corrosion inhibitor tryptophan molecular dynamics simulation DFT calculation dense adsorption

Received: 25 March 2025 32134.14.1005.4537.2025.098

ZTFLH:

TQ015.9

Fund: National Natural Science Foundation of China(52374026);National Natural Science Foundation of China(51974351);Shandong Provincial Natural Science Foundation(ZR2024ME125)

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	BAI Ruiyu
	HUANG Wei'an
	JIA Jianghong
	ZHANG Yanming
	LIU Yunfeng
	WANG Zengbao

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https://www.jcscp.org/EN/10.11902/1005.4537.2025.098 OR https://www.jcscp.org/EN/Y2026/V46/I1/261

Fig.1 Molecular structure of histidine (a), phenylalanine (b), proline (c), tryptophan (d) and tyrosine (e)

Fig.2 Geometrically optimized structures of histidine (a), phenylalanine (b), proline (c), tryptophan (d) and tyrosine (e)

Fig.3 HOMO (left), LUMO (middle) orbital and electrostatic potential (ESP) distribution of histidine (a), phenylalanine (b), proline (c), tryptophan (d) and tyrosine (e)

Table 1 Related parameter values of quantum computing of cyclic amino acids

Fig.4 Fukui function index of histidine (a), phenylalanine (b), proline (c), tryptophan (d) and tyrosine (e)

Fig.5 Conformation before (left) and after (right) adsorption on Fe(110) surface of histidine (a), phenylalanine (b), proline (c), tryptophan (d) and tyrosine (e)

Table 2 Interaction adsorption energy and binding energy between cyclic amino acids and Fe(110) surface

Fig.6 Mean square displacement plots of H⁺ (a) and Cl^-(b) diffusion in the blank H₂O phase and adsorbed amino acid film phase

Table 3 Diffusion coefficients of corrosive substances (H⁺, Cl^-) in H₂O phase and amino acid molecular membrane phase

Fig.7 DFT simulation error bar graph of amino acid molecules in HOMO (a) and LUMO (b)

Fig.8 MD simulation error bar chart of amino acid molecules on Fe(110) surface

Fig.9 Electrochemical results of N80 steel in 20%HCl solution with and without amino acids: (a) Nyquist plots, (b) Bode plots, (c) Bode phase diagram, (d) potentiodynamic polarization curves

Fig.10 Equivalent circuit diagram of EIS spectra

Table 4 Impedance parameters of N80 steel containing different amino acids in 20%HCl

Table 5 PDP parameters of N80 carbon steel without and with non-amino acids in 20%HCl

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