Opening of an icosahedral boron framework: A combined infrared spectroscopic and computational study

Fagiani, Matias Ruben; Liu, Lei; Esser, Tim K.; Gabel, Detlef; Heine, Thomas; Asmis, Knut R.; Warneke, Jonas

doi:10.1016/j.cplett.2015.02.030

Cited by 25 publications

(23 citation statements)

References 47 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For example, aB 12 clusterw as confirmed to be ab owl-shaped quasi-planar structure, but it preferred to be a3 Dc age structure when more seven iodine atoms were substituted. [19][20][21] The earlier 2D-to-3D transitioni na nionic boron clusters also occurs upon addition of transition metals. For instance, B 16 À is aq uasi-planar cluster [6] with as ymmetry of C 2h , whereas CoB 16 À is at ubular-like cluster.…”

Section: Introductionmentioning

confidence: 99%

“…Upon substitution with halogen atoms, this 2D‐to‐3D structural transition occurs earlier with fewer boron atoms. For example, a B 12 cluster was confirmed to be a bowl‐shaped quasi‐planar structure, but it preferred to be a 3D cage structure when more seven iodine atoms were substituted . The earlier 2D‐to‐3D transition in anionic boron clusters also occurs upon addition of transition metals.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Understanding the Central Location of a Hexagonal Hole in a B₃₆ Cluster

Liu

Osorio

Heine

2016

Chemistry An Asian Journal

Self Cite

View full text Add to dashboard Cite

The most stable form of a B cluster has a central hexagonal hole. Such an interesting finding has led to the possible synthesis of a 2D boron sheet by employing the B cluster as the building unit. Herein, a DFT study to investigate the reason for the central location of the hexagonal hole in the B cluster is presented. The results show that the B cluster with a central hexagonal hole is highly thermodynamically and kinetically stable. More importantly, such high stability is further understood through chemical bonding analysis.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Understanding the Central Location of a Hexagonal Hole in a B₃₆ Cluster

Liu

Osorio

Heine

2016

Chemistry An Asian Journal

Self Cite

View full text Add to dashboard Cite

show abstract

“…Recently, a new series of perhalogenated B 12 X 12 2– (X = F, Cl, Br, I) clusters have been prepared and studied ,, that show unusual gas-phase reactivity when subjected to collisions in an ion trap mass spectrometer. Sequential removal of iodine from B 12 I 12 2– showed that the cage structure begins to break , and becomes planar when seven iodine atoms are left. In the process, B 12 I 9 – is formed when I – is removed from B 12 I 10 2– .…”

mentioning

confidence: 99%

Like Charges Attract?

Zhao

Zhou

Wang

et al. 2016

J. Phys. Chem. Lett.

View full text Add to dashboard Cite

Using multiscale first-principles calculations, we show that two interacting negatively charged B 12 I 9 − monoanions not only attract, in defiance of the Coulomb's law, but also the energy barrier at 400 K is small enough that these two moieties combine to form a stable B 24 I 18 2− moiety. Ab initio molecular dynamics simulations further confirm its stability up to 1500 K. Studies of other B 12 X 9 − (X = Br, Cl, F, H, Au, CN) show that while all of these B 24 X 18 2− moieties are stable against dissociation, the energy barrier, with the exception of B 24 Au 18 2− , is large so as to hinder their experimental observation. Our results explain the recent experimental observation of the "spontaneous" formation of B 24 I 18 2− in an ion trap. A simple model based upon electrostatics shows that this unusual behavior is due to competition between the attractive dipole−dipole interaction caused by the aspherical shape of the particle and the repulsive interaction between the like charges.

show abstract

“…In the solid state, boron compounds often adopt threedimensional (3D) structures [6][7][8][9][10]. One heavily studied type is boranes of general form B n H n .…”

Section: Planar Boron Clustersmentioning

confidence: 99%

Geometries and Electronic Structures of Boron Clusters: Planar Structures and All-boron Fullerenes

Liu¹

2016

J Apl Theol

View full text Add to dashboard Cite

[5]. Thus, they attract the interests of interdisciplinary researchers. A primary task in the research of boron clusters is to find the most stable structures of clusters containing given numbers and types of atoms. In this mini-review, we summarize the geometries and electronic structures of two commonly studied boron clusters, planar boron clusters and all-boron fullerenes. Planar Boron ClustersIn the solid state, boron compounds often adopt threedimensional (3D) structures [6][7][8][9][10]. One heavily studied type is boranes of general form B n H n . Most of the boranes are shown to be cage-like, referred as deltahedra [11]. The representative example is B 12 H 12 2− , which was first theoretically investigated by Longuet-Higgins and Roberts using molecular orbital theory [12]. They concluded that the B 12 H 12 structure could be stable only as a di-anion, B 12 H 12 2− , having 13 skeletal bonding orbitals and 12 outward pointing external orbitals. This hypothesis was confirmed later by experimental data, and the structure of B 12 H 12 2− anion was shown to be icosahedral [13]. Unlike 3D cage structures, which are the dominant configurations of boron compounds in the solid state, the pure small boron clusters (n ≤ 40) are found to be two-dimensional (2D) planar or quasi-planar in the gas phase, and the chemical bonding analysis suggests that this planarity is a consequence of π bonding in the cluster forms [9,10]. The simplest pure boron cluster is the diatomic B 2 , which serves as the first example of unusual chemical bonding in the boron species. On the basis of Hartree-Fock and UMP4 (unrestricted fourth order Møller-Plesset perturbation theory) calculations [14], the next pure boron cluster, B 3 , is shown to exist in cationic or anionic forms with a triangular structure of D 3h symmetry.In 2004, Zubarev et al concluded that pure boron clusters containing up to 15 atoms retain planar or quasi-planar conformation [15]. However, there still remains a strong interest to determine the critical size at which structural transition from 2D to 3D occurs. This, however, is a challenging task due to the complexity of these systems and the existence of a large number of isomers. Such 2D-to-3D structural transition is also strongly affected by the charges of boron clusters. For cationic boron clusters (B n + ), the largest planar or quasi-planar structure was established for n=15, and the transition from planar to cylindrical structure takes place for B 16 + [16]. Combining experiment (photoelectron spectroscopy) with computational studies (global minimum search), Kiran et al [17]found that the neutral B 20 cluster undergoes a 2D-to-3D structural transition, resulting in formation of a stable double-ring tubular structure with a diameter of 5.2 Å (Figure 1). The tubular structure was considered as the embryo of the thinnest single-walled boron nanotubes.However, the upper limit for the B n − anionic clusters still remains an open question. Through a joint study of photoelectron spectroscopy and ab initio computatio...

show abstract

Opening of an icosahedral boron framework: A combined infrared spectroscopic and computational study

Cited by 25 publications

References 47 publications

Understanding the Central Location of a Hexagonal Hole in a B₃₆ Cluster

Understanding the Central Location of a Hexagonal Hole in a B₃₆ Cluster

Like Charges Attract?

Geometries and Electronic Structures of Boron Clusters: Planar Structures and All-boron Fullerenes

Contact Info

Product

Resources

About

Opening of an icosahedral boron framework: A combined infrared spectroscopic and computational study

Cited by 25 publications

References 47 publications

Understanding the Central Location of a Hexagonal Hole in a B36 Cluster

Understanding the Central Location of a Hexagonal Hole in a B36 Cluster

Like Charges Attract?

Geometries and Electronic Structures of Boron Clusters: Planar Structures and All-boron Fullerenes

Contact Info

Product

Resources

About

Understanding the Central Location of a Hexagonal Hole in a B₃₆ Cluster

Understanding the Central Location of a Hexagonal Hole in a B₃₆ Cluster