Mass spectrometric stability study of binary MSn clusters (S=Si, Ge, Sn, Pb, and M=Cr, Mn, Cu, Zn)

Neukermans, Sven; Wang, Xin; Veldeman, Nele; Janssens, Ewald; Silverans, Roger; Lievens, Peter

doi:10.1016/j.ijms.2005.12.056

Cited by 112 publications

(102 citation statements)

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“…As shown in Table I, E HOMS -E HOMO is not included in the calculations of M@C 60 clusters, because they are not unreasonable structures, and can not also be viewed as superatomic atoms owe to their negative embedding energies (-0.38, -0.90, -0.83 eV for Zn@C 60 , Cd@C 60 and Hg@C 60 clusters, respectively) and larger R shell (3. 12 cluster, the R shell (3.08 Å) obviously less than the sum of the Van Waals radii of Mn and Sn atoms (1.37+2.17=3.54 Å), and the embedding energy (6.89 eV) significantly bigger than the binding energy (2.64 eV), these results suggest that Mn atom is strongly bonded with outer Sn atom, ie., can be attractively embedded to the centre of Sn 12 , which agrees well with previous studies on the same structure. 7,8,14 The similar analyses on all TM@X 12 and M@X 12 clusters, indicate that TM or M atoms can be attractively embedded to the centre of X 12 too, and suggest that their structures also are extremely stable.…”

Section: A Stability Analysismentioning

confidence: 70%

The role of TM’s (M’s) d valence electrons in TM@X12 and M@X12 clusters

2016

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Using the density functional theory method, the icosahedral TM@X12 (M@X12) clusters (TM=Mn, Tc, Re; M=Zn, Cd, Hg; and X=Sn, Ge), which are composed of Sn12 (Ge12) shell covering a single TM (M) atom, have been systematically examined to explore the role of TM’s (M’s) d valence electrons playing in the clusters. The results show that the magnetism originate from the contribution of TM’s d valence electrons to TM@X12 clusters, where TM’s (M’s) d valence electrons are not included in the superatomic electronic states to TM@X12 (M@X12) clusters. Taking into account the structural stability (imaginary frequency, binding energy, embedding energy, and core-shell interaction) as well as the chemical stability (HOMO-LUMO gap) after, we proposed that TM@X12 and M@X12 clusters can be assigned as the protyle superatoms. Furthermore, the results suggest that M@C60 clusters can not be superatoms, because their negative embedding energies and the distance from the center atom (M) to C atom is larger than the sum of their Van Waals radii. Interestingly enough, we may obtain a simple judging method: for a magnetic superatom, the smaller the energy gap between the highest occupied magnetic state (HOMS) and Fermi level or HOMO (MOgap, or MFgap), the easier on the change of its spin magnetic moment.

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Section: A Stability Analysismentioning

confidence: 70%

The role of TM’s (M’s) d valence electrons in TM@X12 and M@X12 clusters

2016

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“…Most of this work has involved the heavy Group 14 element species with the magic cluster size number of 10 and 12. [10][11][12][26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45] The Co@Ge 10 3− and Fe@Ge 10 3− clusters 30,31 feature an encapsulated pentagonal prismatic structure (D 5h ), whereas the isoelectronic Ni@Pb 10 2− cluster 28,29 prefers the encapsulated bicapped square antiprism structure (D 4d ). Gas phase experiments show that the stannaspherene (Sn 12 2− ) and plumbaspherene (Pb 12 2− ) cages can trap the main-group and transition metals or the f-block elements except of potassium.…”

Section: Introductionmentioning

confidence: 99%

Photoelectron velocity-map imaging signature of structural evolution of silver-doped lead Zintl anions

Xie

Qin

et al. 2012

The Journal of Chemical Physics

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A set of silver-doped lead Zintl anions, Ag@Pb n − (n = 5-12), have been studied using photoelectron velocity-map imaging spectroscopy and quantum chemical calculation. The structures of Ag@Pb n − (n = 7-9, 11) built upon a square pyramid base, hitherto not considered, were assigned. Overall agreement between the experimental and calculated photoelectron spectra as well as vertical detachment energies allows for structural evolution to be established. The silver atom prefers to stay outside in the n ≤ 6 clusters and intends to be encapsulated by the lead atoms in n > 6. A stable endohedral cage with bicapped square antiprism structure is formed at n = 10, the endohedral structure of which persists for the larger clusters. Especially, these Ag@Pb n − anions have been found to undergo a transition between square pyramid and pentagonal pyramid molecular structures at n = 11.

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“…However, if there are insufficient Si atoms to fully enclose the dopant atom, basketlike structures are formed [11]. Although mass spectrometry and photodissociation experiments [8,[16][17][18][19] show an enhanced stability of specific transition-metal doped silicon clusters, no single experiment has yet provided detailed information on their structure. Up to now, mainly indirect evidence is found for the formation of symmetric species by photoelectron and x-ray spectroscopy studies [20][21][22] and chemical probe methods [20,23].…”

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confidence: 99%

Structural Identification of Caged Vanadium Doped Silicon Clusters

et al. 2011

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The geometry of cationic silicon clusters doped with vanadium, Si n V þ (n ¼ 12-16), is investigated by using infrared multiple photon dissociation of the corresponding rare gas complexes in combination with ab initio calculations. It is shown that the clusters are endohedral cages, and evidence is provided that Si 16 V þ is a fluxional system with a symmetric Frank-Kasper geometry. DOI: 10.1103/PhysRevLett.107.173401 PACS numbers: 36.40.Mr, 33.20.Ea, 61.46.Bc The ongoing trend towards further miniaturization in microelectronics triggers a quest for nanostructured building blocks. Given the importance of silicon in the semiconductor industry, it is straightforward to consider small silicon particles for nanostructuring. The search for silicon building blocks was initiated in the 1990s and revealed strong size dependencies and cluster geometries that do not correspond to bulk fragments [1]. Unfortunately, elemental silicon clusters have dangling bonds, which renders them chemically reactive and therefore not suitable as nanoscale building blocks [2]. In contrast to carbon, silicon prefers the formation of bonds through sp 3 hybridization, resulting in three-dimensional structures [3]. Ion mobility studies demonstrated that silicon structures follow a prolate growth sequence and no fullerenelike caged particles are formed [4,5]. However, incorporating a metal atom or hydrogenation can saturate the dangling bonds and induce the formation of caged silicon clusters [3,6,7].Theoretical investigations of doped silicon clusters have considered dopants from almost every group of the periodic table [6]. Most interestingly, it is predicted that transition-metal atoms possibly stabilize the clusters and induce the formation of symmetric endohedral cages with the dopant atom at the center of the cage, which is of relevance for novel silicon based nanostructured devices [8][9][10][11][12]. For example, fullerenelike cages and Frank-Kasper (FK) polyhedrons, which are tetrahedrally close-packed structures containing interpenetrating polyhedra with coordination numbers 12, 14, 15, or 16 [13], are predicted for Ti and V doped silicon clusters with at least 12 Si atoms [10,14,15]. However, if there are insufficient Si atoms to fully enclose the dopant atom, basketlike structures are formed [11]. Although mass spectrometry and photodissociation experiments [8,[16][17][18][19] show an enhanced stability of specific transition-metal doped silicon clusters, no single experiment has yet provided detailed information on their structure. Up to now, mainly indirect evidence is found for the formation of symmetric species by photoelectron and x-ray spectroscopy studies [20][21][22] and chemical probe methods [20,23].In this Letter, the structure of size selected endohedrally doped silicon clusters is obtained by combining experimental infrared multiple photon dissociation (IR-MPD) spectroscopy with quantum chemical calculations. It will be shown that the V dopant atom in the cationic Si n V þ (n ¼ 12-16) clusters locates at the center ...

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Mass spectrometric stability study of binary MSn clusters (S=Si, Ge, Sn, Pb, and M=Cr, Mn, Cu, Zn)

Cited by 112 publications

References 40 publications

The role of TM’s (M’s) d valence electrons in TM@X12 and M@X12 clusters

The role of TM’s (M’s) d valence electrons in TM@X12 and M@X12 clusters

Photoelectron velocity-map imaging signature of structural evolution of silver-doped lead Zintl anions

Structural Identification of Caged Vanadium Doped Silicon Clusters

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