Convolutional Neural Networks to Assist the Assessment of Lattice Parameters from X-ray Powder Diffraction.

This article presents the development of convolutional neural networks (CNNs) for the estimation of lattice parameters in organic compounds across various crystal systems. A comprehensive collection of 92,085 organic compounds was utilized to train the CNNs, encompassing crystals with unit cells containing up to 512 atoms and a maximum unit cell volume of 8000 Å3. Simulated diffraction patterns were generated for each compound, comprising four diffraction patterns with different crystal sizes. These diffraction patterns were generated within a 2θ window of 3-60°, employing a step size of 0.02051°. Two distinct CNN architectures were developed with differing input data. The first CNN, referred to as XRD-CNN, was trained solely on diffraction patterns. In the test set, XRD-CNN demonstrated a mean absolute percentage error (MAPE) of 11.04% for unit cell vectors, 7.40% for angles, and 26.83% for unit cell volume. The second CNN, XRDElem-CNN, incorporated a binary representation of atoms within the unit cell as an additional input. XRDElem-CNN achieved improved performance, yielding MAPE values of 4.73% for unit vectors, 6.49% for angles, and 6.05% for the unit cell volume. To validate the performance of XRDElem-CNN, real diffraction patterns obtained from a conventional laboratory diffractometer (Cu Kα wavelength) were employed. Various representations of atoms within the unit cell were proposed, which were computationally efficient for evaluation with the CNNs. The assessed lattice parameters by XRDElem-CNN were validated using the Lp-search method, showing agreement with the reported values.

Evolution of the vibrational spectra of doped hydrogen clusters with pressure.

The evolution of the vibrational spectra of the isoelectronic hydrogen clusters H26, H24He, and H24Li(+) is determined with pressure. We establish the vibrational modes with collective character common to the clusters, identify their individual vibrational fingerprints and discuss frequency shifts in the giga-Pascal pressure region. The results are of interest for the identification of doping elements such as inert He and ionic Li(+) in hydrogen under confinement or, conversely, establish the pressure of doped hydrogen when the vibrational spectrum is known. At high pressure, the spectra of the nanoclusters resemble the spectrum of a solid, and the nanoclusters may be considered crystals of nanometer scale. The computations are performed at the gradient-corrected level of density functional theory. The investigation is the first of its kind.

Pressure-induced metallization of Li+-doped hydrogen clusters.

Endohedrally encapsulated hydrogen clusters doped with inert helium (H24He) and ionic lithium (H24Li(+)) are investigated. The confinement model is a nanoscopic analogue of the experimental compression of solid hydrogen. The structural and electronic properties of the doped hydrogen clusters are determined under the effects of pressure. The results are compared with these of the isoelectronic (pure) hydrogen counterpart H26 under similar physical conditions. Pressure increase rates with respect to H26 of approximately 1.1 are observed with the insertion of helium or lithium. The changes of geometrical structures and HOMO-LUMO gap energies with the pressure point out the pressure-induced metallization of the Li(+)-doped cluster. The computations are done using density functional theory in the form implemented for molecules; they include zero-point energy effects and, to our best knowledge, are the first of their kind.

Equation of state of a model methane clathrate cage.

We investigate the behavior of a model methane clathrate cage under high hydrostatic pressures. The methane clathrate cage consists of 20 water molecules forming 12 pentagonal faces, with a methane molecule positioned at the cage center. The clathrate compound is located inside a fullerene-type arrangement of 180 He atoms to simulate an isotropic pressure. Different pressures are simulated by decreasing the radius of the He array. The minimal energy of the total system for each configuration is calculated by using density functional theory. The variation of the energy with the volume of the imprisoned clathrate cage leads to the proposal of a (cold) equation of state in the pressure range [0,60] GPa. The elastic parameters of the state equation are found in agreement with equivalent quantities measured on clathrates in their sI conformation. Special attention is given to the distribution of the confined atoms and the eventual symmetry lost from the clathrate cage with the pressure, as the clathrate cage constitutes a basic structural unit of the crystal. Finally, the strengths and limitations of the model are discussed.

Effect of Pressure on the Distribution of Electrons in a Cluster of H2S.

We carry out a theoretical study of the effect of pressure on the atomic and electronic distribution of a cluster made of 155 H2S molecules. The pressure was modeled by bringing the cluster into a spherical container made of 500 helium atoms and reducing the diameter of the container. We did ab initio molecular calculations using DFT. At the lowest pressure, the S-H-S angle between two neighboring H2S molecules has a distribution with a mean value of 167.1°. This angle will be shorter as pressure increases, reaching a distribution with a mean value of 125.5° at the highest pressure. Changes in this angle result from a strong S-S interaction, displacing the H atoms from the line joining the sulfur atoms. This rearrangement of the atomic distribution generates hydrogen-rich spatial regions. We analyzed the evolution of Mulliken charges on S and H atoms in the cluster with pressure, finding that electrons move from S to H atoms, suggesting that these hydrogen-rich regions should be responsible for the electrical conductivity and, consequently, also for the superconductivity in solid H2S under pressure.

Cortisol controlled release by mesoporous silica.

In this study four types of SBAs were synthesized and then impregnated with hydrocortisone. One is a straight SBA-15, obtained using Pluronics P123 as structuring agent; two others were modified using 1,3,5-trimethylbenzene as additive, and the fourth one was prepared using sodium iodide as additive. Three of these have in common a p6 mm symmetry with nanotubes packed hexagonally, yet they differ in their functional groups. The fourth sample is basically disordered. The drug release kinetics showed two stages: a fast-rate early stage dominated by the controlled release of the hydrocortisone adsorbed in the macropores of the reservoir, followed by a slow-rate delivery that we assume is controlled by the hydrocortisone diffusion through the nanopores. It is shown that the release kinetics can be strongly influenced by using different co-additives.

Atomic and Electronic Properties of a 155 H2S Cluster under Pressure.

This is an all-electron density functional study of a cluster with 155 H2S molecules subjected to pressures between 0.2 and 681.2 GPa. For modeling pressure, the cluster was in a container made of 500 He atoms. As the pressure increased, the bond length between the atoms decreased. This decrease changed the atomic distribution of the cluster. Initially, the H2S molecules interacted weakly through hydrogen bonds. Then, the pressure moved the H atoms along the axis connecting two sulfur atoms, with S-H bond lengths between 1.4 and 1.6 Å. At high pressures, the atomic distribution consisted of interleaved layers of H and S atoms. The energy density of states of the valence band had two sub-bands with an energy gap between them. The overlapping of the 2a1 molecular orbitals of the H2S molecules determined the molecular orbitals in the low-energy sub-band. In this sub-band, the molecular orbital with the lowest energy has no nodes; at high pressures, it has non-zero values for all the internuclear regions of the cluster. The overlapping of the molecular orbitals 1b2, 3a1, and 1b1 of the H2S molecules determined the orbitals in the high-energy sub-band. The energy band gap (lowest unoccupied molecular orbital-highest occupied molecular orbital) decreased with the pressure, from 5.3906 eV for 0.2 GPa to 0.4980 eV for 681.2 GPa, whereas the gap between the sub-bands decreased from 4.7729 eV for 0.2 GPa to 0.03 eV for pressures higher than 125.5 GPa. The present study provides, from first principles, an idea on the role of hydrogen atoms in the evolution of solid phases of H2S with pressure, which is difficult to obtain from experiments.

Synthesis and characterization of nanocapsules with shells made up of Al13 tridecamers.

The synthesis of samples by the sol-gel method with aluminum tri-sec-butoxide as cation precursor, 2-propanol as solvent, and sulfuric acid as hydrolysis catalyst gave rise to nanocapsules with an average diameter of 20 nm and a shell thickness of 3.5 nm. The analysis of the X-ray diffraction patterns and the 27Al MAS NMR spectra showed that the shell of the nanocapsules was made up of Al13 tridecamers ordered in a noncrystalline symmetry. The interaction between the capsule's shells opened the capsule structure, producing curved fibers, but maintaining the atomic local order. This opening of the capsules favored the reordering of the atomic local order of Al13 tridecamers into the one of crystalline boehmite, when the sample was aged at room temperature for several days; it also increased the pore volume and the specific surface area of the sample. The crystallization transformed the curved fibers into rods made of small crystalline boehmite bars. The capsule morphology was preserved after calcining the nonaged sample at 700 degrees C, indicating that the transformation of the phase made up of ordered Al13 tridecamers into a noncrystalline alumina was pseudomorphic. We describe and partially explain one of the possible atomic ordering evolutions from the one of an isolated Al13 tridecamer, to the phase forming the nanocapsules shell, until eventually coming to the ordering corresponding to boehmite crystalline rods.

Comparison of the Activity and the Stability in CO Oxidation of Au-Cu Catalysts Supported on TiO2 in Anatase or Rutile Phase.

Au-Cu catalysts supported on anatase or rutile phases were prepared by deposition-precipitation method. The titania polymorph used as the support determined the catalytic behavior. For the Au-Cu/rutile catalysts, the metallic phase had smaller dimensions than for the Au-Cu/anatase catalysts. The catalysts supported on anatase, however, were more active and stable than those supported on rutile. A systematic study of the catalytic activity for CO oxidation as a function of the temperature of activation and the aging time was performed. The catalytic properties were correlated with the properties of the catalysts analyzed with X-ray powder diffraction, refinement of the crystalline structures with the Rietveld method, and transmission electron microscopy. When the support was anatase, a pretreatment at 400 degrees C in air led to the most active catalysts, whereas when the support was rutile, a pretreatment between 200 and 300 degrees C in air led to the most active catalysts; activation under hydrogen generated less active catalysts. The Au-Cu catalysts activated in air were more active for the oxidation of CO than the respective monometallic gold catalysts, indicating a promoting effect between gold and copper to catalyze this reaction.

Effect of Anatase Synthesis on the Performance of Dye-Sensitized Solar Cells.

Anatase nanoparticles were synthesized from a titanium isopropoxide solution using a hydrothermal process at different pressures in an autoclave system while keeping the volume of the solution constant. As the autoclave pressure was increased from 1 to 71 atm (23 to 210 °C), the crystal size in the nanoparticles increased from 9 to 13.8 nm. The anatase nanoparticles were used to build dye-sensitized solar cells (DSSC). Mesoporous films of this oxide were deposited over conducting SnO2:F substrates using the screen-printing technique and then annealed at 530 °C at 1 atm of air pressure. The morphology of the mesoporous film surface of anatase, studied using scanning electron microscopy, revealed that the crystal size and pore distribution were functions of the pressure conditions. The energy band gap of the films as a function of the crystal size exhibited quantum effects below 11.8 nm. The effects of the anatase synthesis conditions and properties of the mesoporous film on the DSSC-type solar cell parameters, η%, V OC, J SC, and FF, were also investigated: the mesoporous anatase films prepared at 200 °C (54 atm of pressure in the autoclave) and annealed at 530 °C in air generated the best solar cell, having the highest conversion efficiency.

On the role of Fe3+ ions in FexOy/C catalysts for hydrogen production from the photodehydrogenation of ethanol.

FexOy/C photocatalysts at different iron content were prepared by the incipient wet impregnation method and calcined at 773 K. The photocatalysts were characterized by means of nitrogen adsorption-desorption isotherms, surface fractal dimension, non-local density functional theory, X-ray diffraction, Rietveld refinement and UV-vis spectroscopy. The photocatalytic activity was evaluated using the photodehydrogenation of ethanol as a model reaction for the production of hydrogen. The specific surface areas of FexOy/C substrates, with 15, 20 and 30 wt% iron content, diminished from 638 to 490 m(2)/g, as the iron content increased. X-ray diffraction analysis showed that iron oxides coexist as wustite and magnetite in samples with Fe contents of 15 and 20 wt%; for sample with 30 wt% Fe, wustite, magnetite and hematite phases were observed. The photophysical, textural and structural properties were modified by the hematite phase formed by thermal treatment. The Rietveld refinements denoted changes in occupancy of Fe(3+) and Fe(2+) in FexOy crystallites. A relationship between the Fe(3+) ions content and the reactivity for the hydrogen production from the photodehydrogenation of ethanol (from 1360 to 2125 µmol h(-1)), was evidenced.