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Abstract <p>This work presents a combined density functional theory (DFT) and molecular simulation investigation of the interfacial behavior of four organic additives, saccharin (SAC), sodium dodecyl sulfate (SDS), sodium citrate (SC), and 2-butyne-1,4-diol (BD), commonly used in Zn-Ni alloy electrodeposition. DFT calculations were employed to optimize molecular geometries and to evaluate frontier molecular orbitals, global reactivity descriptors, Fukui functions, and molecular electrostatic potential maps to identify the dominant reactive sites and intrinsic reactivity of each additive. The results show that sodium citrate exhibits the highest theoretical reactivity, characterized by the smallest HOMO–LUMO energy gap and the greatest charge-transfer capability, whereas SAC and BD display more localized reactive centers. To correlate electronic properties with interfacial performance, Monte Carlo and molecular dynamics simulations were carried out in aqueous solution on Fe(110) surfaces over a range of temperatures. These simulations reveal that sodium dodecyl sulfate possesses the strongest adsorption and interaction energies at all investigated temperatures, indicating superior surface affinity and interfacial anchoring, while SAC and BD adsorb stably with lower molecular deformation upon adsorption. The combined results establish a clear structure–reactivity–adsorption relationship and provide a mechanistic ranking of the additives based on reactivity and surface binding. This molecular-level insight explains how specific functional groups regulate nucleation and growth during Zn-Ni electrodeposition and offers a rational basis for optimizing additive formulations to achieve smoother and more protective alloy coatings.</p>

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Density Functional Theory and Molecular Dynamics Study of Organic Additives for Electrodeposited Zn-Ni Alloys

  • 期刊论文

  • 发表日期：

    2026年6月22日

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  • Nazih Ribouh,
  • Yassira Boutaleb,
  • Chems El Acil Kaddeche,
  • Ramzi Jalgham,
  • Fadhel Ismail,
  • Rabah Rehamnia

摘要

Abstract

This work presents a combined density functional theory (DFT) and molecular simulation investigation of the interfacial behavior of four organic additives, saccharin (SAC), sodium dodecyl sulfate (SDS), sodium citrate (SC), and 2-butyne-1,4-diol (BD), commonly used in Zn-Ni alloy electrodeposition. DFT calculations were employed to optimize molecular geometries and to evaluate frontier molecular orbitals, global reactivity descriptors, Fukui functions, and molecular electrostatic potential maps to identify the dominant reactive sites and intrinsic reactivity of each additive. The results show that sodium citrate exhibits the highest theoretical reactivity, characterized by the smallest HOMO–LUMO energy gap and the greatest charge-transfer capability, whereas SAC and BD display more localized reactive centers. To correlate electronic properties with interfacial performance, Monte Carlo and molecular dynamics simulations were carried out in aqueous solution on Fe(110) surfaces over a range of temperatures. These simulations reveal that sodium dodecyl sulfate possesses the strongest adsorption and interaction energies at all investigated temperatures, indicating superior surface affinity and interfacial anchoring, while SAC and BD adsorb stably with lower molecular deformation upon adsorption. The combined results establish a clear structure–reactivity–adsorption relationship and provide a mechanistic ranking of the additives based on reactivity and surface binding. This molecular-level insight explains how specific functional groups regulate nucleation and growth during Zn-Ni electrodeposition and offers a rational basis for optimizing additive formulations to achieve smoother and more protective alloy coatings.