Hui-Yan Zhao

Boron-Double-Ring Sheet, Fullerene, and Nanotubes: Potential Hydrogen Storage Materials

Similar to carbon-based graphene, fullerenes and carbon nanotubes, boron atoms can form sheets, fullerenes, and nanotubes. Here we investigate several of these novel boron structures all based on the boron double ring within the framework of density functional theory. The boron sheet is found to be metallic and flat in its ground state. The spherical boron cage containing 180 atoms is also stable and has I symmetry. Stable nanotubes are obtained by rolling up the boron sheet, and all are metallic. The hydrogen storage capacity of boron nanostructures is also explored, and it is found that Li-decorated boron sheets and nanotubes are potential candidates for hydrogen storage. For Li-decorated boron sheets, each Li atom can adsorb a maximum of 4 H2 molecules with g(d) =7.892 wt %. The hydrogen gravimetric density increases to g(d) =12.309 wt % for the Li-decorated (0,6) boron nanotube.

Cu20Si12: A Hollow Cage Constituted of a Copper Dodecahedron and a Silicon Icosahedron

A stable hollow copper silicide cage with Ih symmetry, Cu20Si12, constituted of a copper dodecahedron and a silicon icosahedron, was investigated using density functional theory. Molecular dynamics simulations show that Cu20Si12 retains its geometric topology up to an effective temperature of about 962 K. The molecule has a HOMO-LUMO gap of 1.099 eV, indicating its relatively high chemical stability. These frontier molecular orbitals show clear characteristics of hybridization between Si 3p and Cu 3d electrons. This proposed structure helps to extend the range of high-symmetry molecular polyhedral species. The hollow space within Cu20Si12 can be used to accommodate other atoms or molecules and emphasizes the benefit of studying endohedral fullerenes.

Wide band gap carbon allotropes: Inspired by zeolite-nets

Based on the topologies proposed for zeolites, six metastable semiconductor carbon allotropes with band gaps of 2.72–3.89 eV are predicted using ab initio density functional calculations. The hardnesses of these allotropes are about 90%–94% that of diamond, indicating that they may be superhard materials. We also present simulated X-ray diffraction spectra of these new carbon allotropes to provide a basis for possible experimental observations and synthesis. These new carbon structures with a range of band gaps and with hardnesses comparable to diamond could be potential targets for the synthesis of hard and transparent materials.

Ti 12 C 68 : A stable T h -symmetry hollow cage

A stable Th-symmetry Ti12C68 cage was systemically investigated using density functional theory. The structure of Ti12C68 is a hollow cage with twelve TiC13 subunit of three pentagons and one hexagon. The calculated frequencies are in the range 95.1 cm−1–1423.9 cm−1. There are no imaginary frequencies, showing its kinetic stability. Ab initio molecular dynamics simulations demonstrate that the topological structure of cage-like Ti12C68 cluster was well maintained when the effective temperature is up to 1139 K. The natural bond orbitals analysis shows that the d orbit of Ti atoms form four σ bonds with the neighboring four carbon atoms in each TiC13 subunit playing an important role in the cluster stability. The molecular frontier orbitals analysis indicates that Ti12C68 cage has a narrow HOMO-LUMO gap with metal-like property. It would be expected to enrich the species of hollow metal carbide clusters.

Hollow Li20B60 Cage: Stability and Hydrogen Storage

A stable hollow Li20B60 cage with D2 symmetry has been identified using first-principles density functional theory studies. The results of vibrational frequency analysis and molecular dynamics simulations demonstrate that this Li20B60 cage is exceptionally stable. The feasibility of functionalizing Li20B60 cage for hydrogen storage was explored theoretically. Our calculated results show that the Li20B60 molecule can adsorb a maximum of 28 hydrogen molecules. With a hydrogen uptake of 8.190 wt% and an average binding energy of 0.336 eV/H2, Li20B60 is a remarkable high-capacity storage medium.

Au20Si12: A hollow Catalan pentakis dodecahedron

A stable hollow Au20Si12 cage with Ih symmetry has been predicted using first-principles density functional theory. The stability of the cage-like Au20Si12 structure is verified by vibrational frequency analysis and molecular dynamics simulations. A relatively large highest occupied molecular orbital-lowest unoccupied molecular orbital gap of 1.057 eV is found. Electronic structure analysis shows that clearly p-d hybridizations between Si atoms and Au atoms are of great importance for the stability of Au20Si12 cage. The cage-like Au20Si12 structure may have potential applications in semiconductor industry and microelectronics.

Eu@Sc20C60: Magnetic Volleyballene*

Recently, a stable hollow Sc20C60 cage with Th point group symmetry has been proposed, due to its volleyballlike shape called volleyballene. Here the structural and electronic properties for Sc20C60 cage with a europium atom are further studied based on density functional theory. The results give two stable low-lying Eu@Sc20C60 isomers, called cage-a and cage-b, respectively, which still retain the cage-like shape of Sc20C60 volleyballene. After a Eu atom is encaged into the Sc20C60 volleyballene, the HOMO—LUMO gaps decrease from 1.47 eV of the Sc20C60 cage to 0.46 eV of cage-a and 0.21 eV of cage-b. Due to the half-filled 4f-electron orbital states of the Eu atom, the two low-lying Eu@Sc20C60 isomers have net magnetic moments of 7μB. This study further provides the possible applications for the Sc20C60 volleyballene, and enriches the species of magnetic cage-like molecules, which provides more information for magnetic storage and magnetic control.

POSSIBLE Si-BASED HALF-METALLIC MATERIALS: MnSi46 CLATHRATES

The structural and magnetic properties of MSi46 (M = Mn, Fe, Co and Ni) clathrates have been studied using density functional theory calculations within the generalized gradient approximation. When the structures involve a dopant at the center of a Si20 or Si24 cage, the results show that the neighboring atoms around the dopant are drawn in toward the center. Some of the silicon clathrates with a Mn or Co dopant at the center site of a Si20 cage, or a Mn, Fe or Ni dopant at the center site of a Si24 cage are found to be half-metallic materials with large magnetic moments, and others with a Fe or Ni dopant at the center site of a Si20 cage or a Co dopant at the center site of a Si24 cage display semi-metallic characters. In particular, MnSi46 with a half-metallic gap of 0.70 eV and a magnetic moment of 5.00 μB shows promise for applications in the field of spintronics.