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<p>We report a comprehensive density functional theory (DFT) study of transition-metal (TM) doped (CdSe)₁₃ nanoclusters, focusing on structural stability, bonding, electronic structure, and magnetism. Substitution of Cd by Mn, Fe, Co, Ni, Cu, Zn, and Hg is examined at two distinct sites. Substitution energies and vibrational frequency analyses confirm that all doped clusters are stable minima, while short molecular dynamics simulations at 300&#xa0;K verify their dynamical robustness. Bond length and Mayer bond order analyses reveal a systematic progression from ionic (Mn) to covalent (Co, Ni, Cu) bonding, with Zn and Hg behaving as nearly inert <i>d</i>¹⁰ dopants. Hirshfeld charges and magnetic moments corroborate this classification, showing strong correlation between charge transfer, bonding covalency, and magnetic spin states. Electronic analysis demonstrates that TM substitution generally narrows the HOMO–LUMO gap relative to pristine (CdSe)₁₃ (~ 2.3&#xa0;eV), enhancing conductivity via LUMO stabilization. Mn and Fe retain relatively large gaps (~ 1.2&#xa0;eV), Co and Ni reduce gaps below 1&#xa0;eV, and Cu produces the most dramatic narrowing (0.41&#xa0;eV, Type A). Zn and Hg preserve host-like gaps (&gt; 2&#xa0;eV), consistent with minimal <i>d–p</i> hybridization. Partial density of states (PDOS) confirm that gap modulation arises from dopant <i>d</i>-orbital participation. These findings establish clear structure–property relationships in TM-doped CdSe nanoclusters, with implications for their design in optoelectronic and spintronic applications.</p> Graphical abstract <p></p>

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Modulating the properties of CdSe nanoclusters by transition-metal doping: a computational study

  • 期刊论文

  • 发表日期：

    2025年11月10日

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  • Jyoti Singh,
  • Rakhi Thareja,
  • Rita Kakkar

摘要

We report a comprehensive density functional theory (DFT) study of transition-metal (TM) doped (CdSe)₁₃ nanoclusters, focusing on structural stability, bonding, electronic structure, and magnetism. Substitution of Cd by Mn, Fe, Co, Ni, Cu, Zn, and Hg is examined at two distinct sites. Substitution energies and vibrational frequency analyses confirm that all doped clusters are stable minima, while short molecular dynamics simulations at 300 K verify their dynamical robustness. Bond length and Mayer bond order analyses reveal a systematic progression from ionic (Mn) to covalent (Co, Ni, Cu) bonding, with Zn and Hg behaving as nearly inert d¹⁰ dopants. Hirshfeld charges and magnetic moments corroborate this classification, showing strong correlation between charge transfer, bonding covalency, and magnetic spin states. Electronic analysis demonstrates that TM substitution generally narrows the HOMO–LUMO gap relative to pristine (CdSe)₁₃ (~ 2.3 eV), enhancing conductivity via LUMO stabilization. Mn and Fe retain relatively large gaps (~ 1.2 eV), Co and Ni reduce gaps below 1 eV, and Cu produces the most dramatic narrowing (0.41 eV, Type A). Zn and Hg preserve host-like gaps (> 2 eV), consistent with minimal d–p hybridization. Partial density of states (PDOS) confirm that gap modulation arises from dopant d-orbital participation. These findings establish clear structure–property relationships in TM-doped CdSe nanoclusters, with implications for their design in optoelectronic and spintronic applications.

Graphical abstract