Geometrical Evolution Pattern and Spectroscopic Properties of Terbium-Doped Germanium Anionic TbGe<i><sub>n</sub></i> (<i>n</i> = 6–17) Nanoclusters: From Tb-Lined to Tb-Encapsulated Structures

Developing advanced materials with enhanced performance through the doping of nanoclusters is a promising strategy. However, there remains an insufficient understanding of the specific effects induced by such doped nanoclusters, particularly regarding the structural evolution pattern after doping wi...

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Main Authors: Chenliang Hao, Jucai Yang
Format: Article
Language:English
Published: MDPI AG 2025-05-01
Series:Molecules
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Online Access:https://www.mdpi.com/1420-3049/30/9/2066
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author Chenliang Hao
Jucai Yang
author_facet Chenliang Hao
Jucai Yang
author_sort Chenliang Hao
collection DOAJ
description Developing advanced materials with enhanced performance through the doping of nanoclusters is a promising strategy. However, there remains an insufficient understanding of the specific effects induced by such doped nanoclusters, particularly regarding the structural evolution pattern after doping with rare-earth elements and their impact on performance. To solve this problem, we used first-principles calculation to study the structural evolution pattern and spectroscopic properties of anionic TbGe<i><sub>n</sub></i> (<i>n</i> = 6–17) nanoclusters through the ABCluster global search technique coupled with the mPW2PLYP double-hybrid density functional theory. The results revealed that the geometrical evolution pattern is from the typical Tb-linked structures (for <i>n</i> = 10–13, in which Tb acts as a linker connecting two germanium sub-clusters) to Tb-centered cage configurations (for <i>n</i> = 14–17). The simulated photoelectron spectroscopy of anionic TbGe<sub>16</sub> agrees well with its experimental counterpart. Furthermore, we calculated properties such as infrared spectroscopy, Raman spectroscopy, ultraviolet–visible (UV–vis) spectra, magnetism, charge transfer, the HOMO-LUMO gap, and relative stability. The results suggest that TbGe<sub>12</sub><sup>−</sup> and TbGe<sub>16</sub><sup>−</sup> clusters, with their remarkable stability and tunable photothermal properties, can serve as ideal building blocks for developing novel functional nanomaterials. These clusters demonstrate promising applications in solar photothermal conversion, photoelectric conversion, and infrared imaging technologies through their distinct one- and three-dimensional architectures, respectively.
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spelling doaj-art-b63c2ad951ab428db12ea5a2a7638a902025-08-20T02:31:20ZengMDPI AGMolecules1420-30492025-05-01309206610.3390/molecules30092066Geometrical Evolution Pattern and Spectroscopic Properties of Terbium-Doped Germanium Anionic TbGe<i><sub>n</sub></i> (<i>n</i> = 6–17) Nanoclusters: From Tb-Lined to Tb-Encapsulated StructuresChenliang Hao0Jucai Yang1Inner Mongolia Key Laboratory of Theoretical and Computational Chemistry Simulation, School of Chemical Engineering, Inner Mongolia University of Technology, Hohhot 010051, ChinaInner Mongolia Key Laboratory of Theoretical and Computational Chemistry Simulation, School of Chemical Engineering, Inner Mongolia University of Technology, Hohhot 010051, ChinaDeveloping advanced materials with enhanced performance through the doping of nanoclusters is a promising strategy. However, there remains an insufficient understanding of the specific effects induced by such doped nanoclusters, particularly regarding the structural evolution pattern after doping with rare-earth elements and their impact on performance. To solve this problem, we used first-principles calculation to study the structural evolution pattern and spectroscopic properties of anionic TbGe<i><sub>n</sub></i> (<i>n</i> = 6–17) nanoclusters through the ABCluster global search technique coupled with the mPW2PLYP double-hybrid density functional theory. The results revealed that the geometrical evolution pattern is from the typical Tb-linked structures (for <i>n</i> = 10–13, in which Tb acts as a linker connecting two germanium sub-clusters) to Tb-centered cage configurations (for <i>n</i> = 14–17). The simulated photoelectron spectroscopy of anionic TbGe<sub>16</sub> agrees well with its experimental counterpart. Furthermore, we calculated properties such as infrared spectroscopy, Raman spectroscopy, ultraviolet–visible (UV–vis) spectra, magnetism, charge transfer, the HOMO-LUMO gap, and relative stability. The results suggest that TbGe<sub>12</sub><sup>−</sup> and TbGe<sub>16</sub><sup>−</sup> clusters, with their remarkable stability and tunable photothermal properties, can serve as ideal building blocks for developing novel functional nanomaterials. These clusters demonstrate promising applications in solar photothermal conversion, photoelectric conversion, and infrared imaging technologies through their distinct one- and three-dimensional architectures, respectively.https://www.mdpi.com/1420-3049/30/9/2066ground-state structure of anionic germanium clusters doped with terbiumstructural evolution patternsmagnetismsimulated photoelectron spectroscopyUV–vis spectra
spellingShingle Chenliang Hao
Jucai Yang
Geometrical Evolution Pattern and Spectroscopic Properties of Terbium-Doped Germanium Anionic TbGe<i><sub>n</sub></i> (<i>n</i> = 6–17) Nanoclusters: From Tb-Lined to Tb-Encapsulated Structures
Molecules
ground-state structure of anionic germanium clusters doped with terbium
structural evolution patterns
magnetism
simulated photoelectron spectroscopy
UV–vis spectra
title Geometrical Evolution Pattern and Spectroscopic Properties of Terbium-Doped Germanium Anionic TbGe<i><sub>n</sub></i> (<i>n</i> = 6–17) Nanoclusters: From Tb-Lined to Tb-Encapsulated Structures
title_full Geometrical Evolution Pattern and Spectroscopic Properties of Terbium-Doped Germanium Anionic TbGe<i><sub>n</sub></i> (<i>n</i> = 6–17) Nanoclusters: From Tb-Lined to Tb-Encapsulated Structures
title_fullStr Geometrical Evolution Pattern and Spectroscopic Properties of Terbium-Doped Germanium Anionic TbGe<i><sub>n</sub></i> (<i>n</i> = 6–17) Nanoclusters: From Tb-Lined to Tb-Encapsulated Structures
title_full_unstemmed Geometrical Evolution Pattern and Spectroscopic Properties of Terbium-Doped Germanium Anionic TbGe<i><sub>n</sub></i> (<i>n</i> = 6–17) Nanoclusters: From Tb-Lined to Tb-Encapsulated Structures
title_short Geometrical Evolution Pattern and Spectroscopic Properties of Terbium-Doped Germanium Anionic TbGe<i><sub>n</sub></i> (<i>n</i> = 6–17) Nanoclusters: From Tb-Lined to Tb-Encapsulated Structures
title_sort geometrical evolution pattern and spectroscopic properties of terbium doped germanium anionic tbge i sub n sub i i n i 6 17 nanoclusters from tb lined to tb encapsulated structures
topic ground-state structure of anionic germanium clusters doped with terbium
structural evolution patterns
magnetism
simulated photoelectron spectroscopy
UV–vis spectra
url https://www.mdpi.com/1420-3049/30/9/2066
work_keys_str_mv AT chenlianghao geometricalevolutionpatternandspectroscopicpropertiesofterbiumdopedgermaniumanionictbgeisubnsubiini617nanoclustersfromtblinedtotbencapsulatedstructures
AT jucaiyang geometricalevolutionpatternandspectroscopicpropertiesofterbiumdopedgermaniumanionictbgeisubnsubiini617nanoclustersfromtblinedtotbencapsulatedstructures