Ab-initio simulation of elastic constants for some ceramic materials

Athermal elasticity for some ceramic materials (α-Al₂O₃, SiC (α and β phases), TiO₂ (rutile and anatase), hexagonal AlN and TiB₂, cubic BN and CaF₂, and monoclinic ZrO₂) have been investigated via density functional theory. Energy-volume equation-of-state computations to obtain the zero pressure equilibrium volume and bulk modulus as well as computations of the full elastic constant tensor of these ceramics at the experimental zero pressure volume have been performed. The present results for the single crystal elasticity are in good agreement with experiments both for the aggregate properties (bulk and shear modulus) and the elastic anisotropy. In contrast, a considerable discrepancy for the zero pressure bulk modulus of some ceramics evaluated from the energy-volume fit to the computational zero pressure volume has been observed.     

A Bloembergen–Purcell–Pound <Superscript>13</Superscript>C NMR relaxation study of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate

The molecular structure and rotational motion of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) were studied over a wide temperature range using the Bloembergen–Purcell–Pound ¹³C NMR spin–lattice relaxation method and NOE factors. Examination of the spin–lattice relaxation times (T ₁) and the rates (R ₁=1/T ₁) of the 1-butyl-3-methylimidazolium cation reveals the relative motions of each carbon in the imidazolium cation. The rotational characteristics of the [BMIM] cation are supported by ab-initio molecular structures of [BMIM][PF6] using density functional theory (DFT) and Hartree–Fock (HF) methods. The ab-initio gas phase structures of [BMIM][PF6] indicate that the 1-butyl-3-methylimidazolium C2 hydrogen, the ring methyl group, and the butyl side-chain hydrogen atoms form hydrogen bonds with the hexafluorophosphate anion.     

Ab-initio molecular dynamics and hybrid explicit-implicit solvation model for aqueous and nonaqueous solvents: GFP chromophore in water and methanol solution as case study

Solute–solvent interactions are proxies for understanding how the electronic density of a chromophore interacts with the environment in a more exhaustive way. The subtle balance between polarization, electrostatic, and non-bonded interactions need to be accurately described to obtain good agreement between simulations and experiments. First principles approaches providing accurate configurational sampling through molecular dynamics may be a suitable choice to describe solvent effects on solute chemical–physical properties and spectroscopic features, such as optical absorption of dyes. In this context, accurate energy potentials, obtained by hybrid implicit/explicit solvation methods along with employing nonperiodic boundary conditions, are required to represent bulk solvent around a large solute–solvent cluster. In this work, a novel strategy to simulate methanol solutions is proposed combining ab initio molecular dynamics, a hybrid implicit/explicit flexible solvent model, nonperiodic boundary conditions, and time dependent density functional theory. As case study, the robustness of the proposed protocol has been gauged by investigating the microsolvation and electronic absorption of the anionic green fluorescent protein chromophore in methanol and aqueous solution. Satisfactory results are obtained, reproducing the microsolvation layout of the chromophore and, as a consequence, the experimental trends shown by the optical absorption in different solvents.     

Anchoring sulphur-headgroup organic molecules at Cu(1 0 0): Tailoring the interface electronic states

Sulphur-headgroup organic molecules have been chemisorbed on Cu(1 0 0) as self-assembled monolayers (SAMs) in highly-ordered two-fold symmetry structures, and the electronic states induced at the interface have been measured by photoemission: a close similarity of the main interface states for methane-thiolate and mercaptobenzoxazole on Cu(1 0 0) in the same p(2 × 2)-phase is observed. The bonding states for methane-thiolate/Cu(1 0 0) in the p(2 × 2) and c(2 × 2) structures have been compared to ab-initio calculation of the total density of states (DOS) for the S/Cu(1 0 0) system in the same phases. The major role of the S-Cu bonding to determine the density of state evolution at the interface is brought to light. The observed differences in the two phases depend mainly on the charge distribution associated to the different molecular packing, with a minor role of the radical group.     

Ab-initio investigations of structural, electronic, magnetic and optical properties of ferromagnetic Cd1-xMnxTe

We report ab-initio calculations of the structural, electronic, magnetic and optical properties of the alloy Cd_1-xMn_xTe as a function of the Mn concentration ‘x’. Ab-initio calculations are based on the density functional theory (DFT) within the generalized gradient approximation (GGA). The calculated lattice constants of the Cd_1-xMn_xTe alloys exhibit Vegard's law downward bowing parameter. For the minority spin channel the Fermi level shifts toward higher energy with the value of ‘x’ in Cd_1-xMn_xTe. The spin-exchange splitting energy Δ_x(d) increases with increasing ‘x’ in Cd_1-xMn_xTe and the values of p-d exchange splitting energy Δ_x(pd) of Cd_1-xMn_xTe show that the effective potential for the minority spin is more attractive than that for the majority spin. The values of exchange constants N₀α and N₀β obtained for Cd_1-xMn_xTe are in agreement with the reported data. The magnetic moment per Mn atom reduces from its free space charge value of 5μ_B to around 4μ_B due to p-d hybridization and this results into an appearance of small local magnetic moments on the non-magnetic Cd and Te sites. The absorption threshold shifts toward higher energy and the static refractive index decreases with the increasing value of ‘x’ in Cd_1-xMn_xTe.     

Spin-polarized structural, electronic and magnetic properties of diluted magnetic semiconductors Cd1−xMnxTe in zinc blende phase

We have investigated the structural, electronic and magnetic properties of the diluted magnetic semiconductor (DMS) Cd_1−xMn_xTe (for x=0.75 and 1.0) in the zinc blende (B3) phase by employing the ab-initio method. Calculations were performed by using the full potential linearized augmented plane wave plus local orbitals (FP-L/APW+lo) method within the frame work of spin-polarized density functional theory (SP-DFT). The electronic exchange-correlation energy is described by generalized gradient approximation (GGA). We have calculated the lattice parameters, bulk modulii and the first pressure derivatives of the bulk modulii, spin-polarized band structures, and total and local densities of states. We estimated the spin-exchange splitting energies Δ_x(d) and Δ_x(pd) produced by the Mn3d states, and we found that the effective potential for the minority spin is more attractive than that of the majority spin. We determine the s-d exchange constant N₀α (conduction band) and p-d exchange constant N₀β (valence band) and these somewhat agree with a typical magneto-optical experiment. The value of calculated magnetic moment per Mn impurity atom is found to be 4.08 μ_B for Cd_0.25Mn_0.75Te and 4.09 μ_B for Cd_0.0Mn_1.0Te. Moreover, we found that p-d hybridization reduces the local magnetic moment of Mn from its free space charge value of 5.0 μ_B and produces small local magnetic moments on the nonmagnetic Cd and Te sites.     

Effect of the final-state interaction on the initial core–hole lifetime: the case of the 4s-hole lifetime of Sn metal

The first theoretical study of the effect of the final-state interaction on the initial core–hole lifetime is presented. The 4s-hole lifetime width of Sn metal is calculated by an ab-initio atomic many-body theory (Green’s function method). When the final-state interaction in the 4p4d two-hole state, created by the 4s⁻¹−4p⁻¹4d⁻¹ f super Coster–Kronig (CK) transition of the initial 4s hole, is explicitly taken into account, the ab-initio atomic many-body calculation of the 4s-hole X-ray photoelectron spectroscopy (XPS) spectrum of Sn atom can provide excellent agreement with experiment in both the 4s-hole energy and the 4s-hole lifetime width. Otherwise, the many-body calculation underestimates considerably the 4s-hole lifetime width. The 4p4d two-hole state interacts strongly with the 4d triple-hole state by the 4p⁻¹4d⁻¹−4d⁻³ f super CK transition. The interaction affects greatly the initial 4s-hole lifetime width.     

Topological controversies in the adaptability concept for glassy germanium selenides

Cluster modelling based on ab-initio calculations testifies lack of intermediate optimally-constrained phase in binary Ge_xSe_100-x system within expected reversibility window (20 ≤ × < 26) in terms of global connectivity. Network of these glasses within 20 ≤ × < 26 compositional range can be composed of over-constrained “outrigger raft” structural motives built of two edge- and four corner-shared GeSe_4/2 tetrahedra interconnected via optimally-constrained ≡ Ge―Se―Se―Ge≡ bridges, extra Se atoms forming ring-like configurations instead of Se―Se dimers.     

Lindemann criterion and the anomalous melting curve of sodium

Recent reports of the melting curve of sodium at high pressure have shown that it has a very steep descent after a maximum of around 1000 K at 31 GPa. This maximum does not occur due to a solid-solid phase transition. According to the Lindemann criterion, this behaviour should be apparent in the evolution of the Debye temperature with pressure. In this work, we have performed an “ab initio” analysis of the behaviour of both the Debye temperature and the elastic constants up to 102 GPa, and find a clear trend at high pressure that should cause a noticeable effect on the melting curve.