Electronic properties of vanadium-doped TiO2.

The electronic properties of vanadium-doped rutile TiO(2) are investigated theoretically with a Hartree-Fock/DFT hybrid approach. The most common oxidation states (V(2+), V(3+), V(4+), and V(5+)) in different spin states are investigated and their relative stability is calculated. The most stable spin states are quartet, quintet, doublet, and singlet for V(2+), V(3+), V(4+), and V(5+) doping, respectively. By comparing the formation energy with respect to the parent oxides and gas-phase oxygen (ΔE), we conclude that V(4+) (ΔE=145.3 kJ mol(-1)) is the most likely oxidation state for vanadium doping with the possibility of V(5+) doping (ΔE=283.5 kJ mol(-1)). The energetic and electronic properties are converged with dopant concentrations in the range of 0.9 to 3.2%, which is within the experimentally accessible range. The investigation of electronic properties shows that V(4+) doping creates both occupied and unoccupied vanadium states in the band gap and V(5+) doping creates unoccupied states at the bottom of the conduction band. In both cases there is a significant reduction of the band gap by 0.65 to 0.75 eV compared to that of undoped rutile TiO(2).

Social Support, Religious Endorsement, and Career Commitment: A Study on Saudi Nurses.

The present study investigates the effect of perceived social support (PSS) and perceived religious endorsement (PRE) on career commitment (CC) of Saudi nurses. The investigation also extends to the moderating role of different demographic and organizational factors in the extent of PSS, and career commitment these nurses report. Data required for meeting these study objectives were collected from male and female Saudi nurses through a structured questionnaire. Multiple regressions using Partial Least Squares based Structural Equation Model, Smart-PLS version 3.0, and independent sample t-test using SPSS version 22.0, were used to analyze data. The study findings reveal that both perceived social support and perceived religious endorsement are important antecedents of career commitment of Saudi nurses. However, private-sector nurses are found to exhibit a significantly higher level of career commitment compared to their public-sector counterparts. Nurses with greater educational attainment perceive higher level of social support and express greater career commitment than their less educated peers. These findings suggest that nursing as a profession should be more openly discussed in both secular and religious contexts, to ensure an adequate level of respect and compassion on behalf of the public. In particular, endorsement from the individual nurses' social networks is vital in maintaining their wellbeing and career commitment. Given the religious influence in all aspects of life in the Saudi society, the current practice of gender-based segregation in Saudi hospitals and clinics seems to be meaningful for sustaining the career commitment of the nurses.

Ionic conductivity of Li2B4O7.

The formation and mobility of Li point defects in Li(2)B(4)O(7) are investigated theoretically with periodic quantum chemical calculations. Calculated defect formation energies obtained with a density functional theory/Hartree-Fock hybrid method and with the Perdew-Wang density functional method are compared. The basis set effect is investigated by comparison of results obtained with atom-centered basis functions and plane waves. With both methods only a moderate relaxation is observed for the atoms surrounding the Li defect position. The defect-induced change of electronic properties is investigated by calculating the density of states for the stoichiometric and defective supercells. The activation energy for the movement of a Li(+) ion along the (001) direction is calculated. It is observed that Li(+) ion migrates through a one-dimensional channel formed by the five-vertex lithium-oxygen (LiO(5)) polyhedra. The calculated activation energies are in excellent accord with experiment.

Theoretical analysis of structural, energetic, electronic, and defect properties of Li2O.

The structural, energetic, and electronic properties of stoichiometric and defective Li(2)O were studied theoretically. The reliability of the Perdew-Wang method in the framework of density functional theory (DFT), and of two DFT/Hartree-Fock hybrid methods (PW1PW and B3LYP), was examined by comparison of calculated and available experimental data. Atom-centered orbitals and plane waves were used as basis functions for the crystalline orbitals. For both cases, the basis set dependence of calculated properties was investigated. With most of the methods, good agreement with the experimental Li(2)O lattice parameter and cohesive energy was obtained. In accordance with experiment, the analysis of electronic properties shows that Li(2)O is a wide gap insulator. Among the considered methods, the hybrid methods PW1PW and B3LYP give the best agreement with experiment for the band gap. The formation of an isolated cation vacancy defect and an F center in Li(2)O were studied. The effect of local relaxation on the calculated defect formation energies and the defect-induced changes of electronic properties were investigated and compared to available experimental results. The migration of a Li(+) ion in Li(2)O bulk was investigated. The activation energy for the migration of a Li(+) ion from its regular tetrahedral site to an adjacent cation vacancy was calculated, including the effect of local relaxation. The calculated activation barriers, 0.27-0.33 eV, are in excellent agreement with experiment.

Structural and electronic properties of Li(2)b(4)O(7).

The reliability of various quantum-chemical approaches for the calculation of bulk properties of lithium tetraborate Li(2)B(4)O(7) was examined. Lattice parameters and the electronic structure obtained with density-functional theory (DFT), with DFT-Hartree-Fock (HF) hybrid methods, and with the semiempirical method MSINDO were compared to available experimental data. We also compared the results at DFT level using different wave functions, either based on linear combinations of atom-centered orbitals (LCAO), or on plane waves, as implemented in the crystalline orbital programs CRYSTAL and VASP. The basis set dependence of calculated properties was investigated for the LCAO method. In the plane wave approach ultrasoft pseudopotentials (US PP), and projector-augmented wave (PAW) potentials were used to represent the core electrons. For all methods under consideration, the calculated Li(2)B(4)O(7) structure parameters are close to each other and agree within a few percent with measured values. A more pronounced method dependence was found for the band structure, the band gap and the cohesive energy. Closest agreement between theoretical and experimental results for the band gap was obtained with the DFT-HF hybrid methods while pure DFT methods underestimate and HF based methods overestimate the measured value. It was found that the calculated band gap strongly depends on the atomic basis set in the LCAO approach. The description of the core electrons considerably affects the cohesive energy obtained with the plane wave approach. Atomic charges based on a Mulliken analysis were compared to effective charges obtained from Raman spectroscopy. Electron density maps are used to analyze the character of B-O and Li-O interactions.

Interstitial lithium diffusion pathways in γ-LiAlO2: a computational study.

Although the Li diffusion in single crystalline γ-LiAlO2 was studied with temperature-dependent Li-7 NMR spectroscopy and conductivity measurements recently, the exact diffusion pathways are not yet clearly identified. Therefore, the present study aims at elucidating the diffusion pathways in γ-LiAlO2 theoretically from first principles. Competing pathways for Li diffusion are investigated using the climbing-image nudged-elastic-band approach with periodic quantum-chemical density functional theory (DFT) method. Li can migrate between two regular LiO4 tetrahedral sites via Li point defect (VLi) and via a Li Frenkel defect (VLi + Lii). On the basis of calculated activation energies for Li diffusion pathways, it is concluded that Li conductivity is strongly dependent on the distribution of Li vacancies and interstitial Li in the lattice. For Frenkel defects where Lii is far away from the migrating Li atom, the calculated activation energies for jumps to nearest-neighbor vacant sites agree with experimental values.

The ionic conductivity in lithium-boron oxide materials and its relation to structural, electronic and defect properties: insights from theory.

We review recent theoretical studies on ion diffusion in (Li(2)O)(x)(B(2)O(3))(1-x) compounds and at the interfaces of Li(2)O :B(2)O(3) nanocomposite. The investigations were performed theoretically using DFT and HF/DFT hybrid methods with VASP and CRYSTAL codes. For the pure compound B(2)O(3), it was theoretically confirmed that the low-pressure phase B(2)O(3)-I has space group P3(1)21. For the first time, the structure, stability and electronic properties of various low-index surfaces of trigonal B(2)O(3)-I were investigated at the same theoretical level. The (101) surface is the most stable among the considered surfaces. Ionic conductivity was investigated systematically in Li(2)O, LiBO(2), and Li(2)B(4)O(7) solids and in Li(2)O:B(2)O(3) nanocomposites by calculating the activation energy (E(A)) for cation diffusion. The Li(+) ion migrates in an almost straight line in Li(2)O bulk whereas it moves in a zig-zag pathway along a direction parallel to the surface plane in Li(2)O surfaces. For LiBO(2), the migration along the c direction (E(A) = 0.55 eV) is slightly less preferable than that in the xy plane (E(A) = 0.43-0.54 eV). In Li(2)B(4)O(7), the Li(+) ion migrates through the large triangular faces of the two nearest oxygen five-vertex polyhedra facing each other where E(A) is in the range of 0.27-0.37 eV. A two-dimensional model system of the Li(2)O :B(2)O(3) interface region was created by the combination of supercells of the Li(2)O (111) surface and the B(2)O(3) (001) surface. It was found that the interface region of the Li(2)O:B(2)O(3) nanocomposite is more defective than Li(2)O bulk, which facilitates the conductivity in this region. In addition, the activation energy (E(A )) for local hopping processes is smaller in the Li(2)O :B(2)O(3) nanocomposite compared to the Li(2)O bulk. This confirms that the Li(2)O:B(2)O(3) nanocomposite shows enhanced conductivity along the phase boundary compared to that in the nanocrystalline Li(2)O.

Insights into Li(+) Migration Pathways in α-Li3VF6: A First-Principles Investigation.

Magnetic, structural, and defect properties of lithium vanadium hexafluoride (α-Li3VF6) are investigated theoretically with periodic quantum chemical methods. It is found that the ferromagnetic phase is more stable than the antiferromagnetic phase. The crystal structure contains three inequivalent Li sites (Li(1), Li(2), and Li(3)), where Li(1) occupies the middle position of the triplet Li(2)-Li(1)-Li(3). The calculated Li vacancy formation energies show that vacancy formation is preferred for the Li(1) and Li(3) sites compared to the Li(2) position. The Li exchange processes between Li(1) ↔ Li(3), Li(1) ↔ Li(2), and Li(2) ↔ Li(3) are studied by calculating the Li(+) migration between these sites using the climbing-image nudged elastic band approach. It is observed that Li exchange in α-Li3VF6 may take place in the following order: Li(1) ↔ Li(3) > (Li(1) ↔ Li(2) > Li(2) ↔ Li(3). This is in agreement with recently published results obtained from 1D and 2D (6)Li exchange nuclear magnetic resonance spectroscopy.

Enhanced conductivity at the interface of Li2O:B2O3 nanocomposites: atomistic models.

A theoretical investigation at density-functional level of Li ion conduction at the interfaces in Li2O:B2O3 nanocomposites is presented. The structural disorder at the Li2O(111):B2O3(001) interface leads to reduced defect formation energies for Li vacancies and Frenkel defects compared to Li2O surfaces. The average activation energy for Li+ diffusion in the interface region is in the range of the values for Li2O. It is therefore concluded that the enhanced Li conductivity of Li2O:B2O3 nanocomposites is mainly due to the increased defect concentration.