Structure and bonding of IrB12−: converting a rigid boron B12 platelet to a Wankel motor

Liu, Lei; Moreno, Diego; Osorio, Edison; Castro, Abril C.; Pan, Sudip; Chattaraj, Pratim Kumar; Heine, Thomas; Merino, Gabriel

doi:10.1039/c6ra02992b

Cited by 70 publications

(57 citation statements)

References 29 publications

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“…In this paper, we examined the result of substituting two or three C atoms into small B 16 and B 19 clusters. Using extensive computation, 20,000 possible configurations were examined in a comprehensive search for the ground state and low-level excited states of C 2 B 14 − and C 3 B 16 .…”

Section: Discussionmentioning

confidence: 99%

“…They found a planar structure, and theoretical calculations showed that the global minimum of B 19 − is a nearly circular planar structure with a central B 6 pentagonal unit bonded to an outer B 13 ring [2]. They also studied B 16 2− with 10 π-electrons, which is an interesting all-boron analogue of naphthalene [3].…”

Section: Introductionmentioning

confidence: 99%

“…Jiménez-Halla et al published the observation of a B 19 − aromatic wankel motor [9]. Internal rotation in B 13 + was studied with chemical bonding analysis [10], and activated with a laser [11].…”

Section: Introductionmentioning

confidence: 99%

“…However, for small clusters, this picture can change. In recent years, there have been investigations of the B 19 and B 19 − clusters, which show striking diffusive behavior as they are heated to 1000 K. We wondered what the effect of substituting a few carbon atoms would be on the properties of these small clusters. To this end, we carried out extensive structural searches and molecular dynamics simulations to study the properties of C 3 B 16 and C 2 B 14 − at elevated temperatures.…”

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confidence: 99%

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Interior Melting of the C3B16 and C2B14− Clusters Between 1000 K and 2000 K

Yang

Ganz

2017

Condensed Matter

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For bulk three-dimensional materials, it is common for the surface to melt at a slightly lower temperature than the bulk. This is known as surface melting, and is typically due to the fact that there are fewer bonds to surface atoms. However, for small clusters, this picture can change. In recent years, there have been investigations of the B 19 and B 19 − clusters, which show striking diffusive behavior as they are heated to 1000 K. We wondered what the effect of substituting a few carbon atoms would be on the properties of these small clusters. To this end, we carried out extensive structural searches and molecular dynamics simulations to study the properties of C 3 B 16 and C 2 B 14 − at elevated temperatures. The ground state structures and lowest energy isomers for these clusters were determined and calculated. The lowest energy structures are two-dimensional with vacancies inside. The C atoms are located in the outer ring in the ground state. At 1400 K, the outer rim containing the carbon atoms has fixed bonding, while the interior atoms are able to diffuse freely. Therefore, both of these clusters display interior melting at 1400 K. This interior melting is explained by the larger bond strength of the rim atoms. Molecular dynamics simulations at 3000 K showed complete melting and we observed a wide variety of configurations in both clusters.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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confidence: 99%

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Interior Melting of the C3B16 and C2B14− Clusters Between 1000 K and 2000 K

Yang

Ganz

2017

Condensed Matter

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“…23 The combination of a PBE0 functional with a def2-TZVP basis set has been widely used to study the electronic structures of boron clusters. 11,17,24 The bonding interactions corresponding to the formation of close-and open-B12X7 − have been analyzed with the EDA scheme. 25 These calculations were performed at PBE0 level with the basis set of TZ2P.…”

Section: Computational Detailsmentioning

confidence: 99%

The effects of halogen elements on the opening of an icosahedral B12 framework

Gong

Osorio

et al. 2017

The Journal of Chemical Physics

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Abstract:The fully halogenated or hydrogenated B12X12 2− (X = H, F, Cl, Br and I) clusters are confirmed to be icosahedral. On the other hand, the bare B12 cluster is shown to have a planar structure. A previous study showed that a transformation from an icosahedron to a plane happens when 5 to 7 iodine atoms are substituted (Chem. Eur. J. 18 (41), 13208-13212).Later, the transition was confirmed to be seven iodine substitutions based on an infrared spectroscopy study (Chem. Phys. Lett. 625,[48][49][50][51][52]. In this study, we investigated the effects of different halogen atoms on the opening of the B12 icosahedral cage by means of density functional theory calculations. We found that the halogen elements do not have significant effects on the geometries of the clusters. The computed IR spectra show similar representative peaks for all halogen substituted clusters. Interestingly, we found a blue-shift in the IR spectra with the increase in the mass of the halogen atoms. Further, we compared the Gibbs free energies at different temperatures for different halogen atoms. The results show that the Gibbs free energy differences between open and close structures of B12X7 − become larger when heavier halogen atoms are present. This interesting finding was subsequently investigated by energy decomposition analysis.Keywords: boron clusters; density functional theory calculations; infrared spectroscopy; Gibbs free energyThe effects of halogen elements on the opening of an icosahedral B12 framework have been investigated by density functional theory calculations and infrared spectroscopy.

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