Designer magnetic superatoms

Reveles, J. Ulises; Clayborne, Andre; Reber, Arthur C.; Pradhan, Kalpataru; Sen, Prasenjit; Pederson, Mark R.

doi:10.1038/nchem.249

Cited by 229 publications

(241 citation statements)

References 42 publications

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“…The variations in the intensity in mass spectra are generally attributable to the experimental conditions. As we are primarily interested in the magnetic character and since our previous theoretical studies had identified VNa 8 to be a magnetic superatom, 17 the negative ion photoelectron spectra were collected for the VNa x − clusters containing 6, 7, 8, and 9 Na atoms. These are shown in Figures 2 and 3.…”

Section: Experimental and Computational Methodsmentioning

confidence: 99%

“…Since the 1D-state has a strong component from the atomic d-state of V, it undergoes a large exchange splitting, leading to a cluster with a spin magnetic moment of 5.0 μ B . 17 Until now, there has been no experimental evidence for the formation of such magnetic states and the nature of the associated ground state.…”

Section: Introductionmentioning

confidence: 99%

“…17 A V atom has a 3d 3 4s 2 valence configuration, while a Na atom is an alkali atom with 3s 1 valence state. A VNa 8 cluster has 13 valence electrons, and the ground-state geometry is a square antiprism of Na atoms with an interior V atom.…”

Section: Introductionmentioning

confidence: 99%

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On the Existence of Designer Magnetic Superatoms

et al. 2013

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The quantum states in small, compact metal clusters are bunched into electronic shells with electronic orbitals resembling those in atoms, enabling classification of stable clusters as superatoms. The filling of superatomic orbitals, however, does not generally follow Hund's rule, and it has been proposed that magnetic superatoms can be stabilized by doping simple metal clusters with magnetic atoms. Here, we present evidence of the existence of a magnetic superatom and the determination of its spin moment. Our approach combines first principles studies with negative ion photoelectron experiments and enables a unique identification of the ground state and spin multiplicity. The studies indicate VNa 8 to be a magnetic superatom with a filled d-subshell and a magnetic moment of 5.0 μ B . Its low electron affinity is consistent with filled subshell and enhanced stability. The synthesis of this species opens the pathway to investigate the spin-dependent electronics of the new magnetic motifs.

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Section: Experimental and Computational Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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On the Existence of Designer Magnetic Superatoms

et al. 2013

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“…Au n (SR) m clusters with a wide range of physical and chemical properties can then be produced. 148,149 In the study for high-resolution separation, we separated large magic Au n (SR) m clusters (n > 100) at high resolution by HPLC using reverse-phase columns. This technique is expected to provide a greater understanding of the size dependence of structural and physical properties for magic Au n (SR) m clusters.…”

Section: Summary and Future Directionsmentioning

confidence: 99%

Toward the Creation of Functionalized Metal Nanoclusters and Highly Active Photocatalytic Materials Using Thiolate-Protected Magic Gold Clusters

Negishi

2013

Bulletin of the Chemical Society of Japan

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Advances in developments in nanotechnology have encouraged the creation of highly functionalized nanomaterials. Thiolate-protected gold clusters (Au n (SR) m ) less than 2 nm in size exhibit size-specific physical and chemical properties not observed in bulk metals. Therefore, they have attracted attention as functional units or building blocks in nanotechnology. The highly stable, magic Au n (SR) m clusters possess great potential as new nanomaterials. We are studying the following subjects related to magic Au n (SR) m clusters: (1) establishing methods to enhance their functionality, (2) developing high-resolution separation methods, and (3) utilizing the clusters as active sites in photocatalytic materials. Through these studies, we aim to create highly functional metal nanoclusters and apply them as highly active photocatalytic materials. The results of our efforts to date are summarized in this paper.

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“…Thus, the Li 3 O + cluster contains 8 valence electrons and corresponds to a magic species in accordance with the 18-electron rule 23,24 . Clearly the closed-shell electron structure is classified as a superatom that consists of specific atoms that share electrons but mimics the chemical behavior of other elements [25][26][27][28][29][30] . However, unlike previous reports of magnetic lithium superatoms that were stretched in three dimensions 31 , Li 3 O + possessed a planar structure while maintaining its superatomic properties.…”

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confidence: 99%

Evolution of lithium clusters to superatomic Li3O+

Pauna

Shi

Huttula

et al. 2017

Applied Physics Letters

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Accurate knowledge of the oxidation stages of lithium is crucially important for developing next-generation Li-air batteries. The intermediate oxidation stages, however, differ in the bulk and cluster forms of lithium. In this letter, using first-principles calculations, we predict several reaction pathways leading to the formation of Li 3 O + superatoms. Experimental results based on time-of-flight mass spectrometry and laser ablation of oxidized lithium bulk samples agreed well with our theoretical calculations. Additionally, the HOMO-LUMO gap of Li 3 O + was close to the energy released in one of these reaction paths, indicating that the superatom could act as a candidate charge-discharge unit.Keywords: Lithium-air battery, laser ablation, superatom, oxidized lithium, Li 3 O Lithium and its compounds are widely used in energy storage materials. Owing to their electrochemical properties, Li-based composites can act as both a good conductor and a semiconductor; switching of the conductivity can be realized by charging and discharging. For example semiconducting lithium peroxide 1 is composed of two equivalent lithium and oxygen atoms 2 . The formation of this compound is undesirable on the surface of lithium battery cathodes 3 ; however, Li 2 O 2 composites plays a key role in large volume Li-air batteries 3-8 . The charge-discharge pathways of Li 2 O 2 have been extensively studied in the determination of suitable battery electrolytes 3,6,8 . To further enlarge the charge-to-mass ratio of batteries, nano-and sub-nano-scale charge carriers are considered to be more capable candidates than their bulk counterparts 9,10 . In contrast to the numerous studies of Li 2 O 2 in the bulk phase, investigations of free Li-O clusters have mainly focused on hyper-lithiated Li 3 O (0,±) clusters. This set of clusters is of particular interest owing to its excess valence electrons. These clusters have been termed "superalkali atoms" in their neutral or charged forms [11][12][13][14] . Although the structure and properties of Li 3 O clusters have been systematically investigated 15 , their formation processes are not yet fully understood. Furthermore, despite many early studies on the thermochemical properties of free Li-O clusters by mass spectrometry 16 , there has been no physical characterization of lithium bulk oxidation states and those of corresponding cluster formations. As building blocks of many nanomaterials with special functionalities 17,18 , Li-based a) E-mail: henri.pauna@oulu.fi b) E-mail: mzhang@ecust.edu.cn clusters also possess unique properties, which could be applied to Li-air batteries 7 . Thus, studies of the formation mechanisms and transformations between Li-O clusters might provide new insights into future energy storage materials.In this letter we report on the evolution and transformation of free lithium clusters to superatomic Li 3 O + . The stability and reaction pathways of Li 3 O + are predicted by first-principles calculations and supported by time-of-flight mass spectrometry (TOFMS) experiments...

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Designer magnetic superatoms

Cited by 229 publications

References 42 publications

On the Existence of Designer Magnetic Superatoms

On the Existence of Designer Magnetic Superatoms

Toward the Creation of Functionalized Metal Nanoclusters and Highly Active Photocatalytic Materials Using Thiolate-Protected Magic Gold Clusters

Evolution of lithium clusters to superatomic Li3O+

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