Bridging the gas and condensed phases for metal-atom encapsulating silicon- and germanium-cage superatoms: electrical properties of assembled superatoms

Yokoyama, Takaho; Nakajima, Atsushi

doi:10.1039/d3cp00120b

Cited by 8 publications

(11 citation statements)

References 126 publications

(249 reference statements)

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“…Evaluating their properties in surface-supported systems is considered a significant contribution beyond gas-phase isolated systems, toward realizing the long-anticipated theoretical predictions concerning cluster-assembled materials, as pointed out by Khanna and Jena . These results suggest that the heteroatom substitution can provide the means to optimally create NC-assembled nanomaterials and freely design their physical properties …”

Section: Discussionmentioning

confidence: 99%

“…66 These results suggest that the heteroatom substitution can provide the means to optimally create NC-assembled nanomaterials and freely design their physical properties. 67 ■ EXPERIMENTAL SECTION Sample Preparation. The sample substrate of deposited Al n B m NCs was fabricated on an organic HB-HBC surface under vacuumkeeping conditions.…”

Section: Reactivity Of B In Almentioning

confidence: 99%

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Oxidative Activation of Small Aluminum Nanoclusters with Boron Atom Substitution prior to Completing the Endohedral B@Al₁₂^– Superatom

Inoue,

Hatanaka,

Nakajima

2023

J. Am. Chem. Soc.

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Elemental substitution and doping validate the optimization of chemical and physical properties of functional materials, and the composition ratio of the substituting atoms generally determines their properties by changing their geometric and electronic structures. For atomically precise nanoclusters (NCs) consisting of countable atom aggregates, the composition can be controlled accurately to provide an ideal model to study the heteroatom substitution effects. Since aluminum (Al) and boron (B) both belong to group 13 in the periodic table, the effect of B atom substitution on Al n NCs can be investigated while maintaining the total number of valence electrons in Al n B m NCs. In this study, oxidative reactivities of small Al NCs with B atom substitution are studied for Al n B m NCs (m = 1, n = 6–14 and m = 2, n = 11) supported on organic surfaces by using X-ray photoelectron spectroscopy and oxygen molecule (O2) exposure measurements. Before completing the endohedral B@Al12 – superatomic NC, one B atom substitution in Al NCs (Al n B) enhances oxidative reactivities 3–20 times compared to those of Al n+1, particularly for n ≤ 11. When one Al atom of Al12B is further substituted by a B atom to form Al11B2, the reactivity drastically increases (6.6 × 102 times), showing that the B atom substitution makes the NC chemically active or inactive geometrically depending on the exohedral or endohedral site for the B atom in the Al NC. In addition, density functional theory calculations show that the electronegative B atom contributes to forming a locally positive Al site to facilitate O2 adsorption except in Al12B, in which the B atom is geometrically shielded by the surface of the Al12 cage in B@Al12.

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Section: Discussionmentioning

confidence: 99%

Section: Reactivity Of B In Almentioning

confidence: 99%

Oxidative Activation of Small Aluminum Nanoclusters with Boron Atom Substitution prior to Completing the Endohedral B@Al₁₂^– Superatom

Inoue,

Hatanaka,

Nakajima

2023

J. Am. Chem. Soc.

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“…16−23 The functional capabilities of nanomaterials assembled from SAs have been theoretically anticipated, 7,8,24 and over the past two decades, experimental advancements in soft-landing techniques have facilitated the construction of new nanoscale assemblies, 25−30 including the assemblies of metal-encapsulating silicon clusters, 16,31 progressing the understanding of their electric conduction properties. 32,33 In the formation of cluster assemblies, not only the designing the property of SAs but also the precise control of interactions with the supporting substrate is crucial, 34 along with ensuring the deposition quantity. Very recently, the preparation of organic substrates has shown superior controllability toward the soft-landing of SAs.…”

Section: ■ Introductionmentioning

confidence: 99%

Alkaline Earth Metal Superatom of W@Si₁₆: Characterization of Group 6 Metal Encapsulating Si₁₆ Cage on Organic Substrates

Terasaka,

Kamoshida,

Ichikawa

et al. 2024

J. Am. Chem. Soc.

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Transition metal atom (M)-encapsulating silicon cage nanoclusters (M@Si 16 ) exhibit a superatomic nature, depending on the central M atom owing to the number of valence electrons and charge state on organic substrates. Since M@Si 16 superatom featuring group 4 and 5 transition metal atoms exhibit rare-gas-like and alkali-like characteristics, respectively, group 6 transition metal atoms are expected to show alkaline earth-like behavior. In this study, M@Si 16 , comprising a central atom from group 6 (M VI = Cr, Mo, and W) were deposited on C 60 substrates, and their electronic and chemical stabilities were investigated in terms of their charge state and chemical reactivity against oxygen exposures. In comparison to alkali-like Ta@Si 16 , the extent of charge transfer to the C 60 substrate is approximately doubled, while the oxidative reactivity is subdued for M VI @Si 16 on C 60 , especially for W@Si 16 . The results show that a divalent state of M VI @Si 16 2+ appears on the C 60 substrate, which is consistently calculated to be a symmetrical cage structure of W@Si 16 2+ in C 3v , revealing insights into the "periodic law" of M@Si 16 superatoms pertaining to the characteristics of alkaline earth metals.

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“…Due to Ta–Si film’s remarkable thermal stability, which can be used to create capacitors and resistors with superior capacitance performance, − tantalum-doped silicon clusters have attracted a lot of attention, especially for Ta@Si 16 superatomic clusters, − which can be used as fundamental building blocks for producing silicon-based nanomaterials. − Furthermore, using the relativistic density functional theory (RDFT) method, the equilibrium geometries, stabilities, and electronic properties of neutral TaSi n ( n = 1–13) and cationic TaSi n + ( n = 1–13) clusters are investigated, , and the optimized geometries of cationic TaSi n + clusters match the experimental data well . Anion photoelectron spectroscopy is used to investigate TaSi n ̅ ( n = 6–17) anions .…”

Section: Introductionmentioning

confidence: 99%

Structural Determination and Bonding Characteristics of the Gas-Phase Ta₂Si₂̅ Anion and Its Neutral: Anion Photoelectron Spectroscopy and Theoretical Studies

Lu,

Liang,

Zhang

et al. 2023

J. Phys. Chem. A

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The structures and bonding characteristics of Ta2Si2̅/0 clusters are investigated using anion photoelectron spectroscopy and quantum chemical calculations. The vertical detachment energy of the Ta2Si2̅ anion is measured to be 2.00 ± 0.08 eV using the 266 nm photon. It is found that the Ta2Si2̅ anion has three low-energy isomers with a C 2v symmetric Ta–Ta dibridged structural framework, all of which contribute to the experimental photoelectron spectrum, while the Ta2Si2 neutral also has a C 2v symmetric Ta–Ta dibridged structural framework. The charge-transfer from Ta atoms to Si atoms is discovered using atomic dipole moment corrected Hirshfeld analysis for the Ta2Si2̅ anion and Ta2Si2 neutral. Chemical bonding investigations show that both the Ta2Si2̅ anion and Ta2Si2 neutral have a strong covalent Ta–Ta bond, as well as σ and π double bonding patterns. Furthermore, the Ta atoms are linked together by a single 2c–2e Ta2 σ bond, whereas the Si atoms are linked together with the Ta atoms via four 2c–2e TaSi σ bonds, two 3c–2e TaSi2 σ bonds, one 4c–2e Ta2Si2 σ bond, and one 4c–2e Ta2Si2 π bond.

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Bridging the gas and condensed phases for metal-atom encapsulating silicon- and germanium-cage superatoms: electrical properties of assembled superatoms

Abstract: With the development of nanocluster (NC) synthesis methods in gas phase, atomically precise NCs composed of finite number of metal and semiconductor atoms have emerged. NCs are expected to be...

Cited by 8 publications

References 126 publications

Oxidative Activation of Small Aluminum Nanoclusters with Boron Atom Substitution prior to Completing the Endohedral B@Al₁₂^– Superatom

Oxidative Activation of Small Aluminum Nanoclusters with Boron Atom Substitution prior to Completing the Endohedral B@Al₁₂^– Superatom

Alkaline Earth Metal Superatom of W@Si₁₆: Characterization of Group 6 Metal Encapsulating Si₁₆ Cage on Organic Substrates

Structural Determination and Bonding Characteristics of the Gas-Phase Ta₂Si₂̅ Anion and Its Neutral: Anion Photoelectron Spectroscopy and Theoretical Studies

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Bridging the gas and condensed phases for metal-atom encapsulating silicon- and germanium-cage superatoms: electrical properties of assembled superatoms

Abstract: With the development of nanocluster (NC) synthesis methods in gas phase, atomically precise NCs composed of finite number of metal and semiconductor atoms have emerged. NCs are expected to be...

Cited by 8 publications

References 126 publications

Oxidative Activation of Small Aluminum Nanoclusters with Boron Atom Substitution prior to Completing the Endohedral B@Al12– Superatom

Oxidative Activation of Small Aluminum Nanoclusters with Boron Atom Substitution prior to Completing the Endohedral B@Al12– Superatom

Alkaline Earth Metal Superatom of W@Si16: Characterization of Group 6 Metal Encapsulating Si16 Cage on Organic Substrates

Structural Determination and Bonding Characteristics of the Gas-Phase Ta2Si2̅ Anion and Its Neutral: Anion Photoelectron Spectroscopy and Theoretical Studies

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Oxidative Activation of Small Aluminum Nanoclusters with Boron Atom Substitution prior to Completing the Endohedral B@Al₁₂^– Superatom

Oxidative Activation of Small Aluminum Nanoclusters with Boron Atom Substitution prior to Completing the Endohedral B@Al₁₂^– Superatom

Alkaline Earth Metal Superatom of W@Si₁₆: Characterization of Group 6 Metal Encapsulating Si₁₆ Cage on Organic Substrates

Structural Determination and Bonding Characteristics of the Gas-Phase Ta₂Si₂̅ Anion and Its Neutral: Anion Photoelectron Spectroscopy and Theoretical Studies