DFT computations combined with semiempirical modeling of variations with temperature of spectroscopic and magnetic properties of Gd3+-doped PbTiO3.

The rare-earth or 3d transition metal dopants in perovskites have potential to induce interesting features, thus opening opportunities for investigations and applications. Hence, understanding some features, i.e., defect structure, site of incorporation, valence state, and mechanism of charge compensation, in a wide range of temperature is crucial for their technological applications. A comprehensive understanding of the mechanism of structural changes in PbTiO3 doped with trivalent rare-earths is significant for their potential applications in photonics. To unravel the structural changes, we utilize the density functional theory (DFT) to optimize structural data, which then serve as input for the semiempirical superposition model (SPM) analysis of spectroscopic and magnetic properties of Gd3+-doped PbTiO3. We compute the formation energies of the doped compounds with and without O-vacancy to determine the stable composition. Analysis of the Bader electron charges computed using DFT plus quantum theory of atoms in molecules enables elucidating the effects of the Gd dopant and O-vacancy on the ionic and covalent bonds and, thereby, chemical stability of the compositions. To explain and corroborate the zero-field splitting parameters (ZFSPs) measured by EMR and the lattice parameter changes obtained from XRD, we employ SPM. The optimized structures obtained from ab initio computations for various structural models of Gd3+ doped PbTiO3 are utilized as input data for SPM calculations of ZFPs. This enables theoretical analysis of variations of ZFSPs from 5 to 780 K. The results were fine-tuned by matching with available experimental EMR data for Gd3+ probes in PbTiO3 nanoparticles. Modeling has been carried out considering several possible structural models and the role of an O-vacancy around Gd3+ centers. The results show that the two-fold modeling approach, combining DFT and SPM, provides a reliable description of experimental data. Comparative analysis indicates that the Ti-site is less favorable for being replaced by Gd3+ with/without O-vacancy. This analysis confirms the plausibility of the Pb2+ site for Gd3+ dopants and sheds light on the changes of crystal structure during the phase transitions occurring in PbTiO3 with decreasing temperature.

Understanding the effect of structural changes on slow magnetic relaxation in mononuclear octahedral copper(II) complexes.

Current advances in molecular magnetism are aimed at the construction of molecular nanomagnets and spin qubits for their utilization as high-density data storage materials and quantum computers. Mononuclear coordination compounds with low spin values of S = ½ are excellent candidates for this endeavour, but knowledge of their construction via rational design is limited. This particularly applies to the single copper(II) spin center, having been only recently demonstrated to exhibit slow relaxation of magnetisation in the appropriate octahedral environment. We have thus prepared a unique organic scaffold that would allow one to gain in-depth insight into how purposeful structural differences affect the slow magnetic relaxation in monometallic, transition metal complexes. As a proof-of-principle, we demonstrate how one can construct two, structurally very similar complexes with isolated Cu(II) ions in an octahedral ligand environment, the magnetic properties of which differ significantly. The differences in structural symmetry effects and in magnetic relaxation are corroborated with a series of experimental techniques and theoretical approaches, showing how symmetry distortions and crystal packing affect the relaxation behaviour in these isolated Cu(II) systems. Our unique organic platform can be efficiently utilized for the construction of various transition-metal ion systems in the future, effectively providing a model system for investigation of magnetic relaxation via targeted structural distortions.

Evaluation of Phytochemical Compositions and Biological Properties of Achillea gypsicola at Different Phenological Stages.

Phytochemicals, which are commonly found at different levels in many medicinal plants, are natural strong antioxidants used in traditional medicine. In this research, determination of differences of phytochemical compositions and biological properties were aimed as periodically (pre-, full and post flowering) and daily (6 am, 1 pm and 8 pm) in Achillea gypsicola Hub.-Mor. The volatile oils belonging to A. gypsicola were obtained by hydrodistillation and analyzed by gas chromatography-flame ionization detection (GC-FID) and gas chromatography-mass spectrometry (GC/MS). The antimicrobial activities of the volatile oils were determined with disc diffusion method. The microdilution method was used to determine minimum inhibitory concentration (MIC). Total phenolic and flavonoid contents were determined by spectrophotometric methods and antioxidant capacities were evaluated by 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical, reducing power (RP) and metal chelating activity (MCA) assay. In addition, the phenolic acid and flavonoid compositions were evaluated by reversed phase-high-performance liquid chromatography (RP-HPLC). This study presented a comprehensive report for the first time on evaluation of the phytochemical composition and the biological properties of A. gypsicola at different phenological stages. Thirty-two compounds, containing the major component as camphor, 1,8-cineole and borneol, were detected. Designated harvest time for the highest yield of volatile oils was found to be at full flowering stage-1 pm. It has been observed that the volatile oil composition changes periodically and even daily. Also, in this research, menthol and menthone were found as the composition of volatile oil in Achillea species for the first time. Full flowering stage was found as the richest period in terms of phenolic acid and flavonoid compositions of A. gypsicola for the first time. The species examined in this research showed a high antioxidant and antimicrobial activity in comparison to other studies with Achillea species. The volatile oils exhibited high performances with range of inhibition zones (8.3-42.3 mm) and minimum inhibitory concentration values (2.25-144 µg/ml). Besides, a high correlation between antioxidant activity and phenolic content of A. gypsicola was found. These results suggest that A. gypsicola can be used as a safe source in the cosmetic, food and pharmaceutical industries.

Tuning the electronic properties of the γ-Al2O3 surface by phosphorus doping.

Tuning the electronic properties of oxide surfaces is of pivotal importance, because they find applicability in a variety of industrial processes, including catalysis. Currently, the industrial protocols for synthesizing oxide surfaces are limited to only partial control of the oxide's properties. This is because the ceramic processes result in complex morphologies and a priori unpredictable behavior of the products. While the bulk doping of alumina surfaces has been demonstrated to enhance their catalytic applications (i.e. hydrodesulphurization (HDS)), the fundamental understanding of this phenomenon and its effect at an atomic level remain unexplored. In our joint experimental and computational study, simulations based on Density Functional Theory (DFT), synthesis, and a variety of surface characterization techniques are exploited for the specific goal of understanding the structure-function relationship of phosphorus-doped γ-Al2O3 surfaces. Our theoretical calculations and experimental results agree in finding that P doping of γ-Al2O3 leads to a significant decrease in its work function. Our computational models show that this decrease is due to the formation of a new surface dipole, providing a clear picture of the effect of P doping at the surface of γ-Al2O3. In this study, we uncover a general paradigm for tuning support-catalyst interactions that involves electrostatic properties of doped γ-Al2O3 surface, specifically the surface dipole. Our findings open a new pathway for engineering the electronic properties of metal oxides' surfaces.

Spectroscopic study for a chromium-adsorbed montmorillonite.

Samples of purified montmorillonite with trace amounts of quartz were subjected to different concentrations of chromium sulphate solutions for one week to allow cation exchange. The chromium-bearing montmorillonites were verified and tested using powder X-ray diffractometry (XRD), X-ray fluorescence spectrometry, electron spin resonance (ESR) spectrometry and Fourier transformation infrared (FTIR) spectroscopy to explore the occupation sites of the chromium. The ESR spectra recorded before and after the chromium exchange show clear differences: a strong and broad resonance with two shoulders at the lower magnetic field side was present to start, and its intensity as well as that of the ferric iron resonance, increased with the concentration of added chromium. The signals introduced by the chromium, for example at g=1.975 and 2.510 etc., suggested that the chromium had several occupational sites. The ESR peak with g=2.510 in the second derivative spectrum suggested that Cr3+ was weakly bounded to TOT with the form of [Cr(H2O)3]3+ in hexagonal cavities. This was verified by comparing the FTIR spectra of the pure and modified montmorillonite. The main resonance centred at g=1.975 indicated that the majority of Cr3+ occupied the interlayer region as [Cr(H2O)6]3+. The substitution of Ca2+ by Cr3+ also greatly affected the vibration of the hydrogens associate to water, ranged from 3500 to 2600cm-1 in FTIR. Furthermore, the presence of two diffraction lines in the XRD results (specifically those with d-values of 1.5171 and 1.2673nm) and the calculations of the size of the interlayer space suggested the presence of two types of montmorillonite with different hydration cations in the sample exposed to 0.2M chromium sulphate. The two diffraction lines were assigned to [Cr(H2O)6]3+ and [Cr(H2O)3O3]3+, respectively. This also suggested that the species of hydration cation was constrained by the concentration of the chromium solution.

Local coordination of Fe3+ in ZnO nanoparticles: multi-frequency electron paramagnetic resonance (EPR) and Newman superposition model analysis.

Iron-doped ZnO nanoparticles have been synthesized through high-energy ball milling of powders produced by the co-precipitation method. Fine particles with an average size down to 40 nm have been obtained after 15 min of milling. Fe(3+) cations have been incorporated into the ZnO lattice within the limits of the solubility. By using multi-frequency and high-field electron paramagnetic resonance (EPR) we have resolved all electronic transitions for the S = 5/2 high-spin system and have accurately determined the EPR spin-Hamiltonian parameters. By combining data from crystallographic x-ray diffraction and EPR with the semi-empirical Newman superposition model we have found the local configurational position of Fe(3+) and have confirmed the symmetry of the lattice. Results presented in this paper indicate that Fe cations most probably substitute at Zn-sites in ZnO. At nanosizes the effect of Fe(3+) cations on the surface becomes remarkable: additional size effects can be observed in the EPR spectrum, which are different from the spectrum of bulk.

A study of the impurity structure for 3d3 (Cr3+ and Mn4+) ions doped into rutile TiO2 crystal.

The local environment around 3d(3) (Cr(3+) and Mn(4+)) ions doped into rutile TiO(2) crystals has been investigated using superposition model (SPM) analysis. The zero-field splitting (ZFS) parameters (ZFSPs) D and E are modeled for the Cr(3+) and Mn(4+) ions at both the substitutional Ti sites with local symmetry orthorhombic D(2h) and the interstitial sites (ISs) with the same symmetry. Several model parameter sets are adopted so as to acquire the best agreement between the calculated ZFSPs and those measured by electron magnetic resonance (EMR). The feasible values of the structural distortions (ΔR(Y), ΔR(XZ) and Δθ) resulting from dopant Cr(3+) and Mn(4+) ions are determined. As a result, it is confirmed that Mn(4+) ions substitute for Ti(4+) sites in rutile TiO(2) crystal; however, it is suggested that Cr(3+) ions may replace at not only Ti(4+) site but also IS.

Investigations of zero-field splitting (ZFS) and local distortion parameters of Fe3+ ions doped into three oxi-spinels (ZnAl2O4, MgAl2O4, and ZnGa2O4) by theoretical analysis.

The local environment around the paramagnetic centers formed by the Fe(3+) ions doped into three oxi-spinel crystals (ZnAl(2)O(4), MgAl(2)O(4), and ZnGa(2)O(4)) is investigated utilizing the fourth-order perturbation formula of the axial zero-field splitting parameter D on the basis of the dominant spin-orbit coupling mechanism. In order to fix a plausible cubic space group for B-sites located by Al(3+)/Ga(3+) cations, several modeling approaches are used and the results are discussed in detail.

Investigations of zero-field splitting (ZFS) and local distortion parameters of ZnAl2S4:Mn2+ by theoretical analysis.

Fourth-order perturbation formula on the basis of the dominant spin-orbit coupling mechanism is employed to investigate the local environment around Mn2+ centers in ZnAl2S4 single crystals. The zero-field splitting (ZFS) parameter D is calculated for the Mn2+ ions at the Al3+ site with local symmetry D3d using the different orbital reduction factors. Both the contributions of the lattice distortions to the crystal-field (CF) parameters and the D are examined by means of different cases. The comparison between the calculated results in this study and the previous experimental and theoretical values reveals a good agreement and reasonable distortion parameters for Mn2+ ions at Al3+ sites.