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First-row transition metal doped germanium clusters Ge(16)M: some remarkable superhalogens

A theoretical study of geometric and electronic structures, stability and magnetic properties of both neutral and anionic Ge(16)M(0/−) clusters with M being a first-row 3d transition metal atom, is performed using quantum chemical approaches. Both the isoelectronic Ge(16)Sc(−) anion and neutral Ge(1...

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Autores principales: Nguyen, Huu Tho, Cuong, Ngo Tuan, Lan, Ngo Thi, Tung, Nguyen Thanh, Nguyen, Minh Tho, Tam, Nguyen Minh
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9068264/
https://www.ncbi.nlm.nih.gov/pubmed/35527729
http://dx.doi.org/10.1039/d1ra08527a
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author Nguyen, Huu Tho
Cuong, Ngo Tuan
Lan, Ngo Thi
Tung, Nguyen Thanh
Nguyen, Minh Tho
Tam, Nguyen Minh
author_facet Nguyen, Huu Tho
Cuong, Ngo Tuan
Lan, Ngo Thi
Tung, Nguyen Thanh
Nguyen, Minh Tho
Tam, Nguyen Minh
author_sort Nguyen, Huu Tho
collection PubMed
description A theoretical study of geometric and electronic structures, stability and magnetic properties of both neutral and anionic Ge(16)M(0/−) clusters with M being a first-row 3d transition metal atom, is performed using quantum chemical approaches. Both the isoelectronic Ge(16)Sc(−) anion and neutral Ge(16)Ti that have a perfect Frank–Kasper tetrahedral T(d) shape and an electron shell filled with 68 valence electrons, emerge as magic clusters with an enhanced thermodynamic stability. The latter can be rationalized by the simple Jellium model. Geometric distortions from the Frank–Kasper tetrahedron of Ge(16)M having more or less than 68 valence electrons can be understood by a Jahn–Teller effect. Remarkably, DFT calculations reveal that both neutral Ge(16)Sc and Ge(16)Cu can be considered as superhalogens as their electron affinities (≥3.6 eV) exceed the value of the halogen atoms and even that of icosahedral Al(13). A detailed view of the magnetic behavior of Ge(16)M(0/−) clusters shows that the magnetic moments of the atomic metals remain large even when they are quenched upon doping. When M goes from Sc to Zn, the total spin magnetic moment of Ge(16)M(0/−) increases steadily and reaches the maximum value of 3 μ(B) with M = Mn before decreasing towards the end of the first-row 3d block metals. Furthermore, the IR spectra of some tetrahedral Ge(16)M are also predicted.
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spelling pubmed-90682642022-05-05 First-row transition metal doped germanium clusters Ge(16)M: some remarkable superhalogens Nguyen, Huu Tho Cuong, Ngo Tuan Lan, Ngo Thi Tung, Nguyen Thanh Nguyen, Minh Tho Tam, Nguyen Minh RSC Adv Chemistry A theoretical study of geometric and electronic structures, stability and magnetic properties of both neutral and anionic Ge(16)M(0/−) clusters with M being a first-row 3d transition metal atom, is performed using quantum chemical approaches. Both the isoelectronic Ge(16)Sc(−) anion and neutral Ge(16)Ti that have a perfect Frank–Kasper tetrahedral T(d) shape and an electron shell filled with 68 valence electrons, emerge as magic clusters with an enhanced thermodynamic stability. The latter can be rationalized by the simple Jellium model. Geometric distortions from the Frank–Kasper tetrahedron of Ge(16)M having more or less than 68 valence electrons can be understood by a Jahn–Teller effect. Remarkably, DFT calculations reveal that both neutral Ge(16)Sc and Ge(16)Cu can be considered as superhalogens as their electron affinities (≥3.6 eV) exceed the value of the halogen atoms and even that of icosahedral Al(13). A detailed view of the magnetic behavior of Ge(16)M(0/−) clusters shows that the magnetic moments of the atomic metals remain large even when they are quenched upon doping. When M goes from Sc to Zn, the total spin magnetic moment of Ge(16)M(0/−) increases steadily and reaches the maximum value of 3 μ(B) with M = Mn before decreasing towards the end of the first-row 3d block metals. Furthermore, the IR spectra of some tetrahedral Ge(16)M are also predicted. The Royal Society of Chemistry 2022-05-04 /pmc/articles/PMC9068264/ /pubmed/35527729 http://dx.doi.org/10.1039/d1ra08527a Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/
spellingShingle Chemistry
Nguyen, Huu Tho
Cuong, Ngo Tuan
Lan, Ngo Thi
Tung, Nguyen Thanh
Nguyen, Minh Tho
Tam, Nguyen Minh
First-row transition metal doped germanium clusters Ge(16)M: some remarkable superhalogens
title First-row transition metal doped germanium clusters Ge(16)M: some remarkable superhalogens
title_full First-row transition metal doped germanium clusters Ge(16)M: some remarkable superhalogens
title_fullStr First-row transition metal doped germanium clusters Ge(16)M: some remarkable superhalogens
title_full_unstemmed First-row transition metal doped germanium clusters Ge(16)M: some remarkable superhalogens
title_short First-row transition metal doped germanium clusters Ge(16)M: some remarkable superhalogens
title_sort first-row transition metal doped germanium clusters ge(16)m: some remarkable superhalogens
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9068264/
https://www.ncbi.nlm.nih.gov/pubmed/35527729
http://dx.doi.org/10.1039/d1ra08527a
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