Strain induced band gap deformation of H/F passivated graphene and h-BN sheet

Strain induced band gap deformations of hydrogenated/fluorinated graphene and hexagonal BN sheet have been investigated using first principles density functional calculations. Within harmonic approximation, the deformation is found to be higher for hydrogenated systems than for the fluorinated systems. Interestingly, our calculated band gap deformation for hydrogenated/fluorinated graphene and BN sheets are positive, while those for pristine graphene and BN sheet are found to be negative. This is due to the strong overlap between nearest neighbor {\pi} orbitals in the pristine sheets, that is absent in the passivated systems. We also estimate the intrinsic strength of these materials under harmonic uniaxial strain, and find that the in-plane stiffness of fluorinated and hydrogenated graphene are close, but larger in magnitude as compared to those of fluorinated and hydrogenated BN sheet.Comment: Submitted to PR

Questioning the existence of a unique ground state structure for Si clusters

Density functional and quantum Monte Carlo calculations challenge the existence of a unique ground state structure for certain Si clusters. For Si clusters with more than a dozen atoms the lowest ten isomers are close in energy and for some clusters entropic effects can change the energetic ordering of the configurations. Isotope pure configurations with rotational symmetry and symmetric configurations containing one additional isotope are disfavored by these effects. Comparisons with experiment are thus difficult since a mixture of configurations is to be expected at thermal equilibrium

Observation of plaquette fluctuations in the spin-1/2 honeycomb lattice

Quantum spin liquids are materials that feature quantum entangled spin correlations and avoid magnetic long-range order at T = 0 K. Particularly interesting are two-dimensional honeycomb spin lattices where a plethora of exotic quantum spin liquids have been predicted. Here, we experimentally study an effective S=1/2 Heisenberg honeycomb lattice with competing nearest and next-nearest neighbor interactions. We demonstrate that YbBr$_3$ avoids order down to at least T=100 mK and features a dynamic spin-spin correlation function with broad continuum scattering typical of quantum spin liquids near a quantum critical point. The continuum in the spin spectrum is consistent with plaquette type fluctuations predicted by theory. Our study is the experimental demonstration that strong quantum fluctuations can exist on the honeycomb lattice even in the absence of Kitaev-type interactions, and opens a new perspective on quantum spin liquids.Comment: 32 pages, 7 Figure

Crystal Structures and Electronic Properties of Haloform-Intercalated C60

Using density functional methods we calculated structural and electronic properties of bulk chloroform and bromoform intercalated C60, C60 2CHX3 (X=Cl,Br). Both compounds are narrow band insulator materials with a gap between valence and conduction bands larger than 1 eV. The calculated widths of the valence and conduction bands are 0.4-0.6 eV and 0.3-0.4 eV, respectively. The orbitals of the haloform molecules overlap with the $\pi$ orbitals of the fullerene molecules and the p-type orbitals of halogen atoms significantly contribute to the valence and conduction bands of C60 2CHX3. Charging with electrons and holes turns the systems to metals. Contrary to expectation, 10 to 20 % of the charge is on the haloform molecules and is thus not completely localized on the fullerene molecules. Calculations on different crystal structures of C60 2CHCl3 and C60 2CHBr3 revealed that the density of states at the Fermi energy are sensitive to the orientation of the haloform and C60 molecules. At a charging of three holes, which corresponds to the superconducting phase of pure C60 and C60 2CHX3, the calculated density of states (DOS) at the Fermi energy increases in the sequence DOS(C60) < DOS(C60 2CHCl3) < DOS(C60 2CHBr3).Comment: 11 pages, 7 figures, 4 table

Geometry and diameter dependence of the electronic and physical properties of GaN nanowires from first principles

We present a comprehensive first-principles investigation of the atomic and electronic structures of gallium nitride nanowires, and examine the dependence on nanowire diameter and shape. We consider nanowires in the 0001 growth direction, with diameters ranging from 8 to 35 and investigate the influence of saturating the dangling bonds at the edges of nanowires. We find that unsaturated nanowires are semiconducting and contain dangling bond states in the region of the band gap, the positions of which remain rather constant with varying diameter. Saturating the nanowires with hydrogen removes these states, and the band gap decreases with increasing nanowire diameter. For the unsaturated wires there is a considerable contraction of the Ga-N bond lengths at the edge of the wires of 6.0%?7.4%, while for saturated wires it is 1.5%. We also calculate the heat of formation of the nanowires and find that as the diameter of the nanowire increases, the average relative stability of the nanowire increases, as intuitively expected

Systematic computation of crystal field multiplets for X-ray core spectroscopies

We present a new approach to computing multiplets for core spectroscopies, whereby the crystal field is constructed explicitly from the positions and charges of surrounding atoms. The simplicity of the input allows the consideration of crystal fields of any symmetry, and in particular facilitates the study of spectroscopic effects arising from low symmetry environments. The interplay between polarization directions and crystal field can also be conveniently investigated. The determination of the multiplets proceeds from a Dirac density functional atomic calculation, followed by the exact diagonalization of the Coulomb, spin-orbit and crystal field interactions for the electrons in the open shells. The eigenstates are then used to simulate X-ray Absorption Spectroscopy and Resonant Inelastic X-ray Scattering spectra. In examples ranging from high symmetry down to low symmetry environment, comparisons with experiments are done with unadjusted model parameters as well as with semi-empirically optimized ones. Furthermore, predictions for the RIXS of low-temperature MnO and for Dy in a molecular complex are proposed.Comment: Accepted for publication in Phys. Rev.

Electronic structure and physical properties of the spinel-type phase of BeP2N4 from all-electron density functional calculations

Using density-functional-theory-based ab initio methods, the electronic structure and physical properties of the newly synthesized nitride BeP2N4 with a phenakite-type structure and the predicted high-pressure spinel phase of BeP2N4 are studied in detail. It is shown that both polymorphs are wide band-gap semiconductors with relatively small electron effective masses at the conduction-band minima. The spinel-type phase is more covalently bonded due to the increased number of P-N bonds for P at the octahedral sites. Calculations of mechanical properties indicate that the spinel-type polymorph is a promising superhard material with notably large bulk, shear, and Young’s moduli. Also calculated are the Be K, P K, P L3, and N K edges of the electron energy-loss near-edge structure for both phases. They show marked differences because of the different local environments of the atoms in the two crystalline polymorphs. These differences will be very useful for the experimental identification of the products of high-pressure syntheses targeting the predicted spinel-type phase of BeP2N4

Evolution of the interfacial structure of LaAlO3 on SrTiO3

The evolution of the atomic structure of LaAlO3 grown on SrTiO3 was investigated using surface x-ray diffraction in conjunction with model-independent, phase-retrieval algorithms between two and five monolayers film thickness. A depolarizing buckling is observed between cation and oxygen positions in response to the electric field of polar LaAlO3, which decreases with increasing film thickness. We explain this in terms of competition between elastic strain energy, electrostatic energy, and electronic reconstructions. The findings are qualitatively reproduced by density-functional theory calculations. Significant cationic intermixing across the interface extends approximately three monolayers for all film thicknesses. The interfaces of films thinner than four monolayers therefore extend to the surface, which might affect conductivity