Electronic structure of gadolinium-doped ceria system: A DFT study

We report a combined anion photoelectron spectroscopy and density functional theory (DFT) study on a series of iron monoxide clusters, FenO (n=2–6). Well-resolved photoelectron spectra were obtained for FenO− at variable detachment energies, allowing the ground state and numerous low-lying excited states of FenO to be observed. Sharp threshold photoelectron features were obtained for each species, which suggest rather small geometry changes between the anion and neutral ground states for the monoxide clusters and allows the electron affinities of the neutral clusters to be measured accurately. Extensive DFT calculations using the generalized gradient approximation were carried out for both FenO and FenO−. Optimized geometries of the ground and lowest excited states of both the anion and neutral species are reported along with the ground-state vibrational frequencies and fragmentation energies. Theoretical electron affinities were compared with the experimental measurements to verify the ground states of the iron monoxide clusters obtained from the DFT calculations.

Lead-free A2ZrX6 “defect” perovskites hold significant potential for many optoelectronic applications due to their stability and tunable properties. Extending a previous work, we present a first-principles density functional theory (DFT) study, utilizing PBE and HSE06 functionals, to systematically investigate the impact of A-site cation and X-site halogen substitutions on the structural and electronic properties of these materials. We varied the A-site cation, considering ammonium, methylammonium, dimethylammonium, trimethylammonium, and phosphonium, and the X-site halogen, trying Cl, Br, and I. Our calculations reveal that both these substitutions significantly affect the band gap and the lattice parameters. Increasing A-site cation size generally enlarges the unit cell, while halogen electronegativity directly correlates with the band gap, yielding the lowest values for iodine-containing systems. We predict a broad range of band gaps (from ~4.79 eV for (PH4)2ZrCl6 down to ~2.11 eV for MA2ZrI6 using HSE06). The (PH4)2ZrX6 compounds maintain cubic crystal symmetry, unlike the triclinic of the ammonium-derived systems. Finally, our calculations show that the MA cation yields the smallest band gap among the ones studied, a result that is attributed to its size and the charges of the hydrogen atoms attached to nitrogen. Thus, our findings offer crucial theoretical insights into A2ZrX6 structure–property relationships, demonstrating how A-site cation and halogen tuning enables control over electronic and structural characteristics, thus guiding future experimental efforts for tailored lead-free perovskite design.

The optoelectronics performances of two-dimensional Cu-doped SnO2 nanosheets were investigated by first-principles calculations on the basis of density functional theory (DFT) and experiments. First, the crystal structures of Cu-doped SnO2 were built and analyzed by using DFT within the generalized gradient approximation (GGA). The total energy of Cu-doped SnO2 was discussed qualitatively and quantitatively from three aspects: charge density, band structure, and state density. The results show that copper doping has little effect on the charge density distribution because of the similar ionic radius of Cu2+, Sn4+, and the close bond lengths of Cu–O and Sn–O. The calculation results of band structure and state density show that the doping of a copper acceptor leads to the appearance of a new energy level at the top of the valence band and decreases the band gap of SnO2. With the guidance of theoretical calculation, the nanosheets of Cu-doped SnO2 are constructed experimentally, and their optoelectronics performances are investigated. The experimental results exhibit that the Cu atom replaces the Sn atom in the SnO2 lattice, while the Cu-doped SnO2 retains the original rutile phase of the intrinsic SnO2. The sample with a doping ratio of 12.5% has more uniform particle morphology and dispersion characteristics. In addition, the 12.5% Cu-doped SnO2 obtained the largest transient photocurrent of 3 μA/cm2 and the lowest resistance to charge transfer, thereby indicating that the material has a remarkably higher optoelectronics performance under this ratio. The theoretical calculation and experimental results are consistent, which indicates that Cu doping effectively enhances the charge transfer in SnO2 and enables it for high-quality application in optoelectronic catalysis.

Experimental results have shown that palladium complexes with chelating aryl- and alkyl-substituted bis-NHC ligands, including [(H3C-Im)2CH2]PdBr2, [(C6H5-Im)2CH2]PdBr2, and [(H3CO-C6H4-Im)2CH2]PdBr2 are excellent catalysts for the Mizoroki-Heck reaction. To better understand and improve the catalysts, a density functional theory (DFT) study of the Heck reaction has been performed at the B3LYP/6-31G* level of theory, complemented by M06/def2-TZVP single-point calculations. Different mechanistic pathways have been investigated and compared to available experimental results. The most likely mechanism is a cationic catalytic cycle involving the palladium oxidation states 0 and +II. We also looked at other oxidation states, but on the basis of the calculated Gibbs free energy a +II/+IV mechanism can be excluded. Aryl substitution with electron-donating groups at the para position (e.g., the methoxy group in [(H3CO-C6H4-Im)2CH2]PdBr2) was found to reduce the reaction barrier of the rate-determining step. This is in agreement with the experimental findings for the catalysts. The experimentally observed cis selectivity could also be explained by the DFT study.

In this study, we report the electronic structure properties of SmFe2 and HoCo2 binary Laves phase compounds using the density functional theory (DFT) method. We treated the exchange correlation potential with generalized gradient approximation (GGA); in addition, GGA+U (U: Hubbard correction) calculations were applied to describe the correlation effects. At the equilibrium state, the lattice parameter [Formula: see text] is found in favorable agreement with the available data. We also treated the magnetic properties of SmFe2 and HoCo2, respectively; it is shown that the magnetic moment values of Sm and Ho atoms are larger than those of Fe and Ho elements. We note that the GGA with Hubbard correction (U) provides the best description of our systems. We also illustrated the band structures and total and partial densities of states (DOS) of the rare earth-4f (Sm and Ho) and transition metals-3d (Fe and Co) orbitals. For both approximations used, the SmFe2 and HoCo2 binary compounds have a metallic character at the Fermi level. This investigation shows the importance of the treatment of correlated electrons for a clear and accurate description of these binary compounds of the Laves phases family.

Poor electron-related cutting current in graphene-based field-effect transistors (FETs) can be solved by placing a graphene layer over a hexagonal boron nitride (BN) substrate, as established by Giovannetti et al. and other researchers. In order to produce high-quality results, this investigation uses 2 × 2 cells (~2.27% mismatch), given that larger cells lead to more favourable considerations regarding interactions on cell edges. In this case, the substrate-induced band gap is close to 138 meV. In addition, we propose a new material based on graphene on BN in order to take advantage of the wonderful physical properties of both graphene and BN. In this new material, graphene is rotated with respect to BN, and it exhibits a better mismatch, only ~1.34%, than the 1 × 1-graphene/1 × 1-BN; furthermore, it has a very small bandgap, which is almost zero. Therefore, in the bands, there are electronic states in cone form that are like the Dirac cones, which maintain the same characteristics as isolated graphene. In the first case (2 × 2-graphene/2 × 2-BN), for example, the resulting band gap of 138 meV is greater than Giovannetti’s value by a factor of ~2.6. The 2 × 2-graphene/2 × 2-BN cell is better than the 1 × 1-graphene/BN one because a greater bandgap is an improvement in the cutting current of graphene-based FETs, since the barrier created by the bandgap is larger. The calculations in this investigation are performed within the density functional theory (DFT) theory framework, by using 2 × 2-graphene/2 × 2-BN and 13 × 13-graphene/23 × 23-(0001) BN cells. Pseudopotentials and the generalized gradient approximation (GGA), combined with the Perdew–Burke–Ernzerhof parametrization, were used. Relaxation is allowed for all atoms, except for the last layer of the BN substrate, which serves as a reference for all movements and simulates the bulk BN.

Effect of Ti modification on Structural, Electronic and Electrochemical properties of Li2FeSiO4—A DFT study using FPLAPW approach

Ternary adsorption of Auramine-O, Rhodamine 6G, and Brilliant Green onto Arapaima gigas scales hydroxyapatite: Adsorption mechanism investigation using CCD and DFT studies

1.Introduction Solid oxide fuel cells (SOFCs) have received much attention as promising electrochemical power generation devices because of their high electrical efficiency and environment adaptability. Development of SOFCs is now focused on lowering the operating temperature from the conventional range of 750-900°C to an intermediate range of 500-700ºC, allowing a wider range of materials for SOFC components and improvement of thermal reliability. Preparing the Yttlia Stabilized Zirconia (YSZ) and Gadolinia-doped ceria (GDC)) bilayer electrolytes are effective for reducing operating temperature [1]. In the present work, NiO-YSZ anode supported cells with YSZ/GDC bilayer electrolytes and (La,Sr) (Co,Fe) O3 (LSCF) thin film cathodes were fabricated by pulsed laser deposition (PLD) and screen printing. However, one thermal cycle test of a cell between 200°C and 600°C, with heating and cooling rates of 400°C /h, resulted in detachment of the LSCF thin film and thus reduced durability. To improve the adhesion between the LSCF and GDC, (La,Sr)CoO3(LSC), nano particles were deposited on the GDC thin films by PLD. This step was expected to increase contact area between electrolyte and cathode. We investigated the influence of the LSC nano particle on thermal reliability and I-V characteristic of SOFCs. 2.Experimental Details NiO-YSZ cermet (NiO:YSZ＝60:40 wt%, 500 μm thick) was used as the anode substrate, YSZ (8 mol% Y2O3) and GDC (10 mol% GdO2) as electrolyte materials, and La0.6Sr0.4Co0.2Fe0.8 (LSCF) and La0.6Sr0.4Co (LSC) as cathode materials. YSZ (8 μm thick) and LSCF (30 μm thick) films were prepared by screen printing and GDC (3 μm thick) was deposited by PLD. Two sets of unit cells were prepared: one set was with LSC nano particles deposited between GDC and LSCF thin films by PLD (NiO-YSZ / YSZ / GDC / LSC particle / LSCF) and the other set was without LSC nano particles (NiO-YSZ / YSZ / GDC / LSCF).Thermal cycle test between 200 and 600°C with heating and cooling rates of 400° C /h were performed. Power densities and I-V characteristics were measured. 3.Results (a) Deposition of LSC nano particles by PLD on the GDC thin film. Figure 1 shows a scanning electron microscopy image of the surface of a GDC thin film. Many LSC nano particles (50-nm diameter) were deposited on the dense GDC thin film by PLD, which increased the area of contact between the GDC and LSCF thin films. (b) Thermal cycle test of NiO-YSZ anode supported cells with or without LSC nano particles. Two types of unit cells, (1) NiO-YSZ / YSZ / GDC / LSC particle / LSCF and (2) NiO-YSZ / YSZ / GDC / LSCF were prepared by screen printing and PLD. Photographs of unit cells after one thermal cycle are shown in Fig. 2. It is evident that adding the LSC nano particles succeeded in suppressing detachment of the LSCF thin film. Spike effect resulted in high adhesion between LSCF and GDC. The unit cell with LSC nano particles survived 50 thermal cycles and yielded higher thermal reliability. (c) I-V characteristics of NiO-YSZ anode supported cells with or without LSC nano particles. Figure 3 shows the I-V characteristics of unit cells with and without LSC nano particles. The maximum power densities of unit cells with or without LSC nano particles were 0.5 and 0.3 W·cm-2, respectively. Cell performances were found to be better when LSC nano particles were deposited, because of increase in reactive sites.[1] T. Mukai et al., Journal of Fuel Cell Science and Technology , 10(2013) 061006-1-6.

Probing the selective salt rejection behavior of thin film composite membranes: A DFT study

Oxygen vacancies are known to critically influence the crystal structure, electronic properties, as well as photocatalytic performance of double perovskites. In this study, we employ first-principles density functional theory (DFT) with generalized gradient approximation (GGA) and Hubbard U corrections to systematically investigate the effects of oxygen vacancies on Ba2CeMO6 (M = Bi, Sb) double perovskites. The introduction of vacancies significantly modifies the band structure, generating intermediate electronic states that reduce the band gap energy and enhance photocatalytic performance, as evidenced by band edge potential analysis. Effective mass calculation supported the results and displayed lighter mass of charge carriers in the reduction potential. Structural relaxations reveal local distortions around the vacancy sites and exhibit vacancy-mediated phase transition phenomenon. The experimental zero band gap of Ba2CeBiO6 is rationalized by the oxygen vacancy-induced semiconducting to metallic electronic configuration. Thermodynamic calculations indicated high Debye temperature and melting point with minimum thermal conductivity. Furthermore, optical property analysis suggests improved light absorption in the visible range, highlighting the potential of defect-engineered Ba2CeMO6 (M = Bi, Sb) for efficient photocatalytic applications. These results provide fundamental insights into defect-mediated property tuning in perovskite semiconductors, offering to design for next-generation functional materials.

Employing the oxidative coupling of phenylacetylene with benzaldehyde as a model reaction, a density functional theory (DFT) study combined with extended X-ray absorption fine structure (EXAFS) experiment was carried out to reveal the difference between dinuclear and mononuclear zinc mediated nucleophilic addition. Newly reported DFT method M11-L computed results suggest that the mononuclear zinc mediated pathway, in which nucleophilic addition occurs via a four-membered ring transition state, is unfavourable both thermodynamically and kinetically. The dinuclear zinc mechanism, which appropriately explains the experimental observations, involves a six-membered ring transition state for nucleophilic addition. Subsequent in situ EXAFS experiment confirmed the existence of dinuclear zinc active species. Moreover, frontier molecular orbital (FMO) analysis and distortion-interaction energy analysis along the whole reaction pathways have provided interpretations for the advantage of dinuclear zinc mediated nucleophilic addition. Consequently, we believe this dinuclear zinc pathway will open up a general consideration of the dinuclear zinc mechanism for nucleophilic additions.

Cholesterol-based dimeric liquid crystals: synthesis, mesomorphic behaviour of frustrated phases and DFT study

Mineral chemistry of metal sulfides

Antispasmodic activity of carnosic acid extracted from rosmarinus officinalis: Isolation, spectroscopic characterization, DFT studies, and in silico molecular docking investigations