{"title":"Modulating the properties of CdSe nanoclusters by transition-metal doping: a computational study","authors":"Jyoti Singh, Rakhi Thareja, Rita Kakkar","doi":"10.1007/s11243-025-00694-y","DOIUrl":null,"url":null,"abstract":"<div><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 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 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 <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><h3>Graphical abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":803,"journal":{"name":"Transition Metal Chemistry","volume":"51 1","pages":""},"PeriodicalIF":2.8000,"publicationDate":"2025-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Transition Metal Chemistry","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s11243-025-00694-y","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
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Abstract
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.
期刊介绍：
Transition Metal Chemistry is an international journal designed to deal with all aspects of the subject embodied in the title: the preparation of transition metal-based molecular compounds of all kinds (including complexes of the Group 12 elements), their structural, physical, kinetic, catalytic and biological properties, their use in chemical synthesis as well as their application in the widest context, their role in naturally occurring systems etc.
Manuscripts submitted to the journal should be of broad appeal to the readership and for this reason, papers which are confined to more specialised studies such as the measurement of solution phase equilibria or thermal decomposition studies, or papers which include extensive material on f-block elements, or papers dealing with non-molecular materials, will not normally be considered for publication. Work describing new ligands or coordination geometries must provide sufficient evidence for the confident assignment of structural formulae; this will usually take the form of one or more X-ray crystal structures.
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