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Extended X-ray absorption fine structure (EXAFS) spectra are sensitive to thermal disorder and are often used to probe local lattice dynamics. Variations in interatomic distances induced by atomic vibrations are described by the temperature-dependent mean-square relative displacement (MSRD), also known as the Debye-Waller factor. In this study, we evaluated the feasibility of addressing the inverse problem, i.e., determining the sample temperature from the analysis of its EXAFS spectrum using the multiple-scattering formalism, considering contributions up to the 4th-7th coordination shell. The method was tested on several monatomic metals (bcc Cr, Mo, and W; fcc Cu and Ag), where the correlated Debye model of lattice dynamics provides a fairly accurate description of thermal disorder effects up to distant coordination shells. We found that the accuracy of the method strongly depends on the temperature range. The method fails at low temperatures, where quantum effects dominate and MSRD values change only slightly. However, it becomes more accurate at higher temperatures, where the MSRD shows a near-linear dependence on temperature.

Understanding interlayer and intralayer coupling in two-dimensional layered materials (2DLMs) has fundamental and technological importance for their large-scale production, engineering heterostructures, and development of flexible and transparent electronics. At the same time, the quantification of weak interlayer interactions in 2DMLs is a challenging task, especially, from the experimental point of view. Herein, we demonstrate that the use of X-ray absorption spectroscopy in combination with reverse Monte Carlo (RMC) and ab initio molecular dynamics (AIMD) simulations can provide useful information on both interlayer and intralayer coupling in 2DLM 2H$_c$-MoS$_2$. The analysis of the low-temperature (10-300 K) Mo K-edge extended X-ray absorption fine structure (EXAFS) using RMC simulations allows for obtaining information on the means-squared relative displacements $\sigma^2$ for nearest and distant Mo-S and Mo-Mo atom pairs. This information allowed us further to determine the strength of the interlayer and intralayer interactions in terms of the characteristic Einstein frequencies $\omega_E$ and the effective force constants $\kappa$ for the nearest ten coordination shells around molybdenum. The studied temperature range was extended up to 1200 K employing AIMD simulations which were validated at 300 K using the EXAFS data. Both RMC and AIMD results provide evidence of the reduction of correlation in thermal motion between distant atoms and suggest strong anisotropy of atom thermal vibrations within the plane of the layers and in the orthogonal direction.

Point defect tolerance in materials, which extends operational lifetime, is essential for societal sustainability, and the creation of a framework to design such properties is a grand challenge in the material sciences. Using three prototypical lead bromide perovskites in single crystal form and high-resolution synchrotron-based X-ray spectroscopy, we reveal the unexpectedly pivotal role of the A-cation in mediating the influence of photoinduced defects. Organic A-cation hydrogen bonding facilitates chemical flexing of the lead-bromide bond that mitigates the self-doping effect of bromide vacancies. The contribution of partially ionic lead-bromide bonding to the electronic band edges, where the bonding becomes more ionic upon the formation of defects, mitigates re-hybridization of the electronic structure upon degradation. These findings reveal two new general design principles for defect tolerance in materials. Our findings uncover the foundations of defect tolerance in halide perovskites and have implications for defect calculations, all beam-based measurements of photophysical properties and perovskite solar cell technology.

Hybrid materials combining an organic matrix and high-Z nanomaterials show potential for applications in radiation detection, allowing unprecedented device architectures and functionality. Herein, novel hybrid organic-inorganic systems were produced using a mixture of tungstate (CaWO$_4$ or ZnWO$_4$) nanoparticles with a P3HT:PCBM blend. The nano-tungstates with a crystallite size of 43 nm for CaWO$_4$ and 30 nm for ZnWO$_4$ were synthesized by the hydrothermal method. Their structure and morphology were characterized by X-ray diffraction and scanning electron microscopy. The hybrid systems were used to fabricate direct conversion X-ray detectors able to operate with zero bias voltage. The detector performance was tested in a wide energy range using monochromatic synchrotron radiation. The addition of nanoparticles with high-Z elements improved the detector response to X-ray radiation compared with that of a pure organic P3HT:PCBM bulk heterojunction cell. The high dynamic range of our detector allows for recording X-ray absorption spectra, including the fine X-ray absorption structure located beyond the absorption edge. The obtained results suggest that nanocrystalline tungstates are promising candidates for application in direct organic-inorganic X-ray detectors.

The chemical states of Ni, Zn, and W in microcrystalline NiWO$_4$-ZnWO$_4$ solid solutions were studied by X-ray photoelectron spectroscopy. The recorded spectra of the Ni 2p, Zn 2p, and W 4f photoelectron lines and Ni L$_2$M$_{23}$M$_{45}$, Zn L$_3$M$_{45}$M$_{45}$, and W N$_4$N$_{67}$N$_{7}$ Auger-transition lines show pronounced changes with increasing Zn concentration. The positions of the resolved photoelectron and Auger-transition lines were combined to construct so-called chemical-state plots (Wagner or Auger-parameter plots) for metal ions in solid solutions. With increasing Zn concentration, the Auger parameter increases for Ni and decreases for W, thus evidencing a lowering and an increase of the electronic polarizability around core-ionized Ni and W ions, respectively. At the same time, the character of Zn-O bonds and the local structure around Zn ions do not change. It is concluded that the dilution of NiWO$_4$ with Zn ions is accompanied by an increase of the Ni-O bond ionicity and an increase of the W-O bond covalency. These changes are attributed to the charge redistribution among [NiO$_6$] and [WO$_6$] structural units. We show that a careful in-depth analysis of XPS data obtained with a laboratory-based X-ray photoelectron spectroscopy system can give chemically sensitive, qualitative information on the changes in the first coordination spheres of each metal ion. This information is otherwise accessible only by synchrotron-based techniques (such as X-ray absorption spectroscopy).

Hot carrier solar cells hold promise for exceeding the Shockley-Queisser limit. Slow hot carrier cooling is one of the most intriguing properties of lead halide perovskites and distinguishes this class of materials from competing materials used in solar cells. Here we use the element selectivity of high-resolution X-ray spectroscopy to uncover a previously hidden feature in the conduction band states, the {\sigma}-{\pi} energy separation, and find that it is strongly influenced by the strength of electronic coupling between the A-cation and bromide-lead sublattice. Our finding provides an alternative mechanism to the commonly discussed polaronic screening and hot phonon bottleneck carrier cooling mechanisms. Our work emphasizes the optoelectronic role of the A-cation, provides a comprehensive view of A-cation effects in the electronic and crystal structures, and outlines a broadly applicable spectroscopic approach for assessing the impact of chemical alterations of the A-cation on halide and potentially non-halide perovskite electronic structure., Comment: 13 pages, 5 figures

The existence of exchange-coupled Ni$^{2+}$ ions -- the so-called magnetic dimers -- in wolframite-type NiWO$_4$ and Zn$_c$Ni$_{1-c}$WO$_4$ solid solutions with high nickel content was discovered by X-ray absorption spectroscopy combined with reverse Monte Carlo (RMC) simulations. Temperature- (10--300 K) and composition-dependent x-ray absorption spectra were measured at the Ni K-edge, Zn K-edge, and W L$_3$-edge of microcrystalline NiWO$_4$, Zn$_c$Ni$_{1-c}$WO$_4$ and ZnWO$_4$. Structural models were obtained from simultaneous analysis of the extended x-ray absorption fine structure (EXAFS) spectra at three metal absorption edges using RMC simulations. The obtained radial distribution functions for different atomic pairs made it possible to trace in detail the changes in the local environment of metal ions and the effect of thermal disorder. Dimerization of Ni$^{2+}$ ions within quasi-one-dimensional zigzag chains of [NiO$_6$] octahedra was evidenced in NiWO$_4$ in the whole studied temperature range. It manifests itself as the splitting of the Ni-Ni radial distribution function into two separate peaks. The effect is further preserved in solid solutions Zn$_c$Ni$_{1-c}$WO$_4$ for $c \leq 0.6$, which is related to the probability to find two Ni$^{2+}$ ions in neighboring positions.

The influence of zinc ions on the thermochromic properties of polycrystalline Cu$_{1-x}$Zn$_x$MoO$_4$ ($x$=0.10, 0.50, 0.90) solid solutions was studied by X-ray absorption spectroscopy at the Cu, Zn and Mo K-edges. Detailed structural information on the local environment of metal ions was obtained from the simultaneous analysis of EXAFS spectra measured at three metal absorption edges using the reverse Monte Carlo method. Thermochromic phase transition with the hysteretic behaviour between $\alpha$ and $\gamma$ phases was observed in Cu$_{0.90}$Zn$_{0.10}$MoO$_4$ solid solution. It was found that the local environment of molybdenum ions is most susceptible to the substitution of copper for zinc and, upon cooling, transforms from tetrahedral MoO$_4$ to distorted octahedral MoO$_6$.

Two boron-rich chalcogenides B12S and B12Se isostructural to {\alpha}-rhombohedral boron were synthesized by chemical reaction of the elements at high-pressure - high-temperature conditions. The crystal structures and stoichiometries of both compounds were confirmed by Rietveld refinement and elemental analysis. The experimental Raman spectra of B12S and B12Se were investigated for the first time. All observed Raman bands have been attributed to the theoretically calculated phonon modes, and the mode assignment has been performed.

Polycrystalline CuMo$_{1-x}$W$_x$O$_4$ solid solutions were studied by resonant X-ray emission spectroscopy (RXES) at the W L$_3$-edge to follow a variation of the tungsten local atomic and electronic structures across thermochromic phase transition as a function of sample composition and temperature. The experimental results were interpreted using ab initio calculations. The crystal-field splitting parameter for the 5d(W)-states was obtained from the analysis of the RXES plane and was used to evaluate the coordination of tungsten atoms. Temperature-dependent RXES measurements were successfully employed to determine the hysteretic behaviour of the structural phase transition between the $\alpha$ and $\gamma$ phases in CuMo$_{1-x}$W$_x$O$_4$ solid solutions on cooling and heating, even at low ($x$<0.10) tungsten content. It was found that tungsten ions have octahedral coordination for in the whole studied temperature range (90-420 K), whereas their coordination changes from tetrahedral to octahedral upon cooling for smaller ($x$ <= 0.15) tungsten content. Nevertheless, some amount of tungsten ions was found to co-exists in the octahedral environment at room temperature for $x$<0.15. The obtained results correlate well with the color change in these solid solutions.

The influence of thermal disorder and static distortions on the local structure in microcrystalline solid solutions of tungstates ZncNi1-cWO4 with c=0.0-1.0 was investigated using temperature-dependent (10-300 K) x-ray absorption spectroscopy (XAS) at the W L3-edge. In addition, the vibrational properties of the solid solutions were studied by Raman spectroscopy. Our results indicate that the formation of solid solutions is accompanied by strong structural relaxations leading to the changes in the [WO6] octahedra distortions, which, in turn, affect the vibrational properties of tungstates. In particular, the frequency and band width of the highest W-O stretching mode at about 900 cm-1 show distinct composition dependence, following the local structure modifications as revealed by XAS.

The contribution of static and thermal disorder is one of the largest challenges for the accurate determination of the atomic structure from the extended X-ray absorption fine structure (EXAFS). Although there are a number of generally accepted approaches to solve this problem, which are widely used in the EXAFS data analysis, they often provide less accurate results when applied to outer coordination shells around the absorbing atom. In this case, the advanced techniques based on the molecular dynamics and reverse Monte Carlo simulations are known to be more appropriate: their strengths and weaknesses are reviewed here.

New boron-rich sulfide B6S and selenide B6Se have been discovered from high pressure - high temperature synthesis combined with ab initio evolutionary crystal structure prediction, and studied by synchrotron X-ray diffraction and Raman spectroscopy at ambient conditions. As it follows from Rietveld refinement of powder X-ray diffraction data, both chalcogenides have orthorhombic symmetry and belongs to Pmna space group. All experimentally observed Raman bands have been attributed to the theoretically calculated phonon modes, and the mode assignment has been performed. Prediction of mechanical properties (hardness and elastic moduli) of new boron-rich chalcogenides have been made using ab initio routines, and both compounds were found to be members of a family of hard phases (Hv ~ 31 GPa).

We have observed enhancement and shift in the spin reorientation transition temperature as a consequence of coexistence of orthorhombic and hexagonal phases and higher aspect ratio in nanoscale LuFeO3. Nanoparticles and nanofibers of LuFeO3 are considered for this work. Nanoparticles have 75 % orthorhombic phase and 25 % hexagonal phase, while nanofibers have 23% orthorhombic phase and 77%-hexagonal phase. Larger aspect ratio in case of nanofibers is seen to help strain-stabilize the hexagonal phase in the material. Magnetic measurements show significant difference in the magnetic behavior and spin reorientation temperature; 183K for the nanoparticle case and 150K for the case of nanofibers. Moreover, the ferromagnetic moment is two order of magnitude higher for nanofibers than that of nanoparticles, In hexagonal phase, frustration of triangular lattice, works against the long range ordering while magnetic anisotropy works in favor of the long range ordering, which contributes towards the enhanced and anomalous magnetic behavior in case of fibers. X -ray absorption near edge spectroscopy (XANES) at the Fe K-edge has been used to probe the symmetry driven dynamics of Fe 3d- 4p orbitals. It established that due to noncentrocymmetry of the Fe atom, the nanofibers have decreased 3d-4p orbital mixing and reduced crystal field splitting energy, which are also contributing factor for the enhanced magnetic behaviour.

High-pressure phase of boron oxide, orthorhombic \b{eta}-B2O3, has been studied in situ by synchrotron X-ray diffraction to 22 GPa and Raman scattering to 46 GPa at room temperature. The bulk modulus of \b{eta}-B2O3 has been found to be 169(3) GPa that is in good agreement with our ab initio calculations. Raman and IR spectra of \b{eta}-B2O3 have been measured at ambient pressure, all experimentally observed bands have been attributed to the theoretically calculated ones, and the mode assignment has been performed. Based on the data on Raman shift as a function of pressure, combined with equation-of-state data, the Gr\"uneisen parameters of all experimentally observed Raman bands have been calculated. \b{eta}-B2O3 enriched by 10B isotope has been synthesized, and the effect of boron isotopic substitution on Raman spectra has been studied.

Raman spectra of rhombohedral boron monosulfide (r-BS) were measured under pressures up to 34 GPa at room temperature. No pressure-induced structural phase transition was observed, while strong pressure shift of Raman bands towards higher wavenumbers has been revealed. IR spectroscopy as a complementary technique has been used in order to completely describe the phonon modes of r-BS. All experimentally observed bands have been compared with theoretically calculated ones and modes assignment has been performed. r-BS enriched by 10B isotope was synthesized, and the effect of boron isotopic substitution on Raman spectra was observed and analyzed.