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Accurate modeling of intermolecular repulsion is an integral component in force field development. Although repulsion can be explicitly calculated by applying the Pauli exclusion principle, this approach is computationally viable only for systems of limited sizes. Instead, it has previously been shown that repulsion can be reformulated in a "classical" picture: the Pauli exclusion principle prohibits electrons from occupying the same state, leading to a depletion of electronic charge between atoms, giving rise to an enhanced nuclear–nuclear electrostatic repulsion. This classical picture is called the isotropic S2/R approximation, where S is the overlap and R is the interatomic distance. This approximation accurately captures the repulsion of isotropic atoms such as noble gas dimers; however, a key deficiency is that it fails to capture the angular dependence of the repulsion of anisotropic molecules. To include directionality, the wave function must at least be a linear combination of s and p orbitals. We derive a new anisotropic S2/R repulsion model through the inclusion of the anisotropic p orbital term in the total wave function. Because repulsion is pairwise and decays rapidly, it can be truncated at a short range, making it amenable for efficient calculation of energy and forces in complex biomolecular systems. We present a parameterization of the S101 dimer database against the ab initio benchmark symmetry-adapted perturbation theory, which yields an rms error of only 0.9 kcal/mol. The importance of the anisotropic term is demonstrated through angular scans of water–water dimers and dimers involving halobenzene. Simulation of liquid water shows that the model can be computed efficiently for realistic system sizes. [ABSTRACT FROM AUTHOR]

The present work shows that the free energy landscape associated with alanine dipeptide isomerization can be effectively represented by specific interatomic distances without explicit reference to dihedral angles. Conventionally, two stable states of alanine dipeptide in vacuum, i.e., C7eq (β-sheet structure) and C7ax (left handed α-helix structure), have been primarily characterized using the main chain dihedral angles, φ (C–N–Cα–C) and ψ (N–Cα–C–N). However, our recent deep learning combined with the "Explainable AI" (XAI) framework has shown that the transition state can be adequately captured by a free energy landscape using φ and θ (O–C–N–Cα) [Kikutsuji et al., J. Chem. Phys. 156, 154108 (2022)]. In the perspective of extending these insights to other collective variables, a more detailed characterization of the transition state is required. In this work, we employ interatomic distances and bond angles as input variables for deep learning rather than the conventional and more elaborate dihedral angles. Our approach utilizes deep learning to investigate whether changes in the main chain dihedral angle can be expressed in terms of interatomic distances and bond angles. Furthermore, by incorporating XAI into our predictive analysis, we quantified the importance of each input variable and succeeded in clarifying the specific interatomic distance that affects the transition state. The results indicate that constructing a free energy landscape based on the identified interatomic distance can clearly distinguish between the two stable states and provide a comprehensive explanation for the energy barrier crossing. [ABSTRACT FROM AUTHOR]

The thermal conductivities of single-/bi-layer graphene and bulk-graphite are obtained using the Boltzmann transport equation (BTE) framework by accounting for three-phonon and four-phonon scatterings. For single-layer graphene, the thermal conductivity and interatomic force constants obtained using temperature-independent finite-difference, and temperature-dependent molecular dynamics-based approaches agree with each other. The use of the thermal snapshot approach to get temperature-dependent force constants results in a non-physical description of interatomic distances for single-layer graphene. The predicted thermal conductivity at room temperature using finite-difference based force constants is 800 W/m K, which is a severe under-prediction of experimentally measured values. For bi-layer graphene and bulk graphite, the thermal snapshot methodology is applicable and thermal conductivity changes by 25% and 5% with temperature-dependent force constants. The effect of four-phonon scattering is less than 10% on the predicted thermal conductivity of bi-layer graphene and graphite, and the obtained thermal conductivities using thermal snapshot methodology are in agreement with the literature. The limitation in the prediction of thermal conductivity of single-layer graphene via the BTE approach stems from non-accountability of temperature-dependence in finite-difference based force constants and non-physical description of interatomic bonds in thermal snapshot based force constants extraction for planar 2-atoms unitcell of single layer graphene. [ABSTRACT FROM AUTHOR]

This study compares results of four relativistic pseudopotential basis sets, which differ mainly by their size: double‐zeta introduced by Hay and Wadt from Los Alamos National Laboratory (LANL2DZ), triple‐zeta based on Stuttgart energy‐consistent scalar‐relativistic pseudopotential (SDD3), its extension with 2fg polarization functions, and combination of Stuttgart pseudopotentials with quintuple‐zeta cc‐pV5Z base (SDD5). Hydrides of transition metals from Cr to Zn group are chosen as reference molecules. The coupled cluster method (CCSD(T)) is used for evaluation of selected molecular characteristics. Interatomic distances, dissociation energies, vibration modes, and anharmonicity constants are determined and compared with available experimental data. As expected, the accuracy of basis depends mainly on its size. However, only moderate modification of SDD3 basis set significantly improves its accuracy, which becomes comparable to the largest basis set. Nevertheless, the time consumption is significantly lower. [ABSTRACT FROM AUTHOR]

This article discusses the synthesis and reactivity of a new sulfonium salt that can transfer a sulfonitrene unit to C=C double bonds. The salt was synthesized on a large scale and is stable in air and water. It was used in two different transformations, expanding indenes to isoquinolines and contracting arylcyclobutenes to cyanocyclopropanes. The reagent is versatile and can tolerate various functional groups, making it a useful tool in skeletal editing. The authors acknowledge funding and provide supporting information for further details. [Extracted from the article]

The amorphous form of poorly soluble drugs is physically unstable and prone to crystallization, resulting in decreased solubility and bioavailability. However, the conventional accelerated stability test for amorphous drugs is time-consuming and inaccurate. Therefore, there is an urgent need to develop rapid and accurate stability assessment technology. This study used the antitumor drug nilotinib free base as a model drug. The degree of disorder and physical stability in the amorphous form was assessed by applying the pair distribution function (PDF) and principal component analysis (PCA) methods based on powder X-ray diffraction (PXRD) data. Specifically, the assessment conditions, such as the PDF interatomic distance range, PXRD detector type, and PXRD diffraction angle range were also optimized. The results showed that more reliable PCA data could be obtained when the PDF interatomic distance range was 0–15 Å. When the PXRD detector was a semiconductor-type detector, the PDF data obtained were more accurate than other detectors. When the PXRD diffraction angle range was 5–40°, the intermolecular arrangement of the amorphous drugs could be accurately predicted. Finally, the accelerated stability test also showed that under the above-optimized conditions, this method could accurately and rapidly assess the degree of disorder and physical stability in the amorphous form of drugs, which has obvious advantages compared with the accelerated stability test. [ABSTRACT FROM AUTHOR]

The potential energy curves (PECs) and spectroscopic constants of the ground and excited states of a LiMg+ molecular cation were investigated. We obtained accurate results for the fifteen lowest-lying states of the LiMg+ cation using the Intermediate Hamiltonian Fock Space Multireference Coupled Cluster (IH-FS-CC) method applied to the (2,0) sector. Relativistic corrections were accounted for using the third-order Douglas–Kroll method. In each instance, smooth PECs were successfully computed across the entire range of interatomic distances from equilibrium to the dissociation limit. The results are in good accordance with previous studies of this molecular cation. Notably, this study marks the first application of IH-FS-CC in investigating a mixed alkali and alkaline earth molecular cation, proving its usability in determining accurate PECs of such diatomics and their spectroscopic constants. [ABSTRACT FROM AUTHOR]

Hard X-ray absorption spectroscopy is a valuable in situ probe for nondestructive diagnostics of metal sites. The low-energy interval of a spectrum (XANES) contains information about the metal oxidation state, ligand type, symmetry and distances in the first coordination shell but shows almost no dependency on the bridged metal-metal bond length. The higher-energy interval (EXAFS), on the contrary, is more sensitive to the coordination numbers and can decouple the contribution from distances in different coordination shells. Supervised machine-learning methods can combine information from different intervals of a spectrum; however, computational approaches for the near-edge region of the spectrum and higher energies are different. This work aims to keep all benefits of XANES and extend its sensitivity towards the interatomic distances in the first and second coordination shells. Using a binuclear bridged copper complex as a case study and cross-validation analysis as a quantitative tool it is shown that the first 170 eVabove the edge are already sufficient to balance the contributions of Cu-O/N scattering and Cu-Cu scattering. As a more general outcome this work highlights the trivial but often overlooked importance of using 'longer' energy intervals of XANES for structural refinement and machine-learning predictions. The first 200 eV above the absorption edge still do not require parametrization of Debye-Waller damping and can be calculated within full multiple scattering or finite difference approximations with only moderately increased computational costs. [ABSTRACT FROM AUTHOR]

The effects of atomic mass in terms of its zero-point vibrational energy, on molar volume, glass transition temperature Tg, and viscosity are studied in glassy and supercooled B2O3 liquids using boron isotope substitutions. The molar volume decreases and Tg and isothermal viscosity increase on the substitution of lighter 10B isotopes with the heavier 11B isotopes. These effects are argued to be a manifestation of the higher zero-point vibrational energy of the lighter isotope, which along with the anharmonicity of the potential well, results in a longer equilibrium inter-atomic distance and larger mean-square displacement with respect to that for the heavier isotope. The isotope effect on viscosity is increasingly enhanced as the temperature approaches Tg, which is shown to be consistent with the prediction of the elastic models of viscous flow and shear relaxation. [ABSTRACT FROM AUTHOR]

This article introduces neural graph distance embedding (nGDE), a method for generating 3D molecular geometries. Leveraging a graph neural network trained on the OE62 dataset of molecular geometries, nGDE predicts interatomic distances based on molecular graphs. These distances are then used in multidimensional scaling to produce 3D geometries, subsequently refined with standard bioorganic forcefields. The machine learning‐based graph distance introduced herein is found to be an improvement over the conventional shortest path distances used in graph drawing. Comparative analysis with a state‐of‐the‐art distance geometry method demonstrates nGDE's competitive performance, particularly showcasing robustness in handling polycyclic molecules—a challenge for existing methods. [ABSTRACT FROM AUTHOR]

Single crystals of the non-stoichiometric YbMn∼0.17Si∼1.89 intermetallic compound were investigated by room-temperature x-ray diffraction as well as by temperature and pressure-dependent x-ray absorption experiments at the Yb L3 edge. The crystal structure can be described in the orthorhombic space group Cmcm or in the non-centrosymmetric P21 monoclinic space group. In both cases, the cell comprises two Yb sites of identical multiplicity with close coordination numbers and interatomic distances. The average Yb valence is found independent of temperature νav ∼ 2.42. Such a low Yb valence is hardly compatible with the occurrence of local magnetism on Yb inferred from a previous study. The pressure dependence of the Yb valence at 10 K does not reveal any first-order transition. The average Yb valence increases continuously under pressure but remains far from trivalency (νav ∼2.63) even under the highest external pressure used of 37 GPa. [ABSTRACT FROM AUTHOR]

Pressure, together with temperature, electric, and magnetic fields, alters the system and allows for the investigation of the fundamental properties of matter. Under applied pressure, the interatomic distances shrink, which modifies the interactions between atoms and may lead to the appearance of new (sometimes exotic) physical properties, such as pressure-induced phase transitions; quantum critical points; new structural, magnetic, and/or superconducting states; and changes of the temperature evolution and symmetry of the order parameters. Muon-spin rotation/relaxation (μ SR) has proven to be a powerful technique in elucidating the magnetic and superconducting responses of various materials under extreme conditions. At present, μ SR experiments may be performed in high magnetic field up to ∼ 9 T, temperatures down to ≃ 10 –15 mK, and hydrostatic pressure up to ∼ 2.8 GPa. In this Perspective, the requirements for μ SR experiments under pressure, the existing high-pressure muon facility at the Paul Scherrer Institute (Switzerland), and selected experimental results obtained by μ SR under pressure are discussed. [ABSTRACT FROM AUTHOR]

The presented main studies of point defects in CdGa2Se4 chalcopyrite are considered to quantify the formation energies of three possible models of Cd, Ga and Se vacancy defects using various local density approximation (LDA) and general gradient approximation (GGA) approximations. Using supercells with 56 atoms, interatomic distances were calculated both for an ideal cell and a supercell containing vacancies. It was found that interatomic distance does not change only in a supercell containing Ga vacancy. Investigation shows that the Ga vacancy has a high defect formation energy (DFE) among other intrinsic vacancies and is therefore unstable. We found that for all vacancies, − 2 charge states are favorable. [ABSTRACT FROM AUTHOR]

Margaritasite is a mineral compound discovered in the early 1980s in Chihuahua, Mexico. It is a natural cesium uranyl vanadate found only, so far, in the Margaritas mine of the Peña Blanca highlands. In this work, a thorough characterization of the aforementioned mineral is presented. The portfolio of the techniques employed includes high-resolution X-ray diffraction, scanning electron microscopy with energy dispersive X-ray spectroscopy, transmission electron microscopy in selected area electron diffraction (SAED) mode, and X-ray absorption spectroscopy (XAS). After extensive data analysis and modeling, new information on the mineral has been retrieved. Its phase composition is margaritasite–carnotite: a solid solution of cesium and potassium uranyl vanadate [(Cs,K)2(UO2)2(VO4)2·nH2O], and margaritasite, which is practically pure cesium uranyl vanadate [Cs2(UO2)2(VO4)2·nH2O]. The crystal structure of both components presents the space group P 1 21/c 1. Yet, each phase has similar, but appreciably different, lattice parameters. The mineral has a lamellar tabular and prismatic morphology. SAED patterns confirm the crystal structure of margaritasite. XAS spectra of Cs, V, and U confirm the elemental composition, oxidation states, and interatomic distances of this structure. These findings are consistent with the presence of cesium in this unique mineral from the paragenesis point of view. [ABSTRACT FROM AUTHOR]

This study investigates the effects of increasing PbO concentration on the Al2O3–PbO–B2O3–SiO2 glasses' physical, mechanical and gamma ray shielding properties. PbO addition leads to higher density and molar mass, making the glass denser. However, molar volume decreases, indicating a more compact structure. Interatomic distances and ion concentration change, strengthening atomic interactions. Oxygen molar volume increases, but packing density drops with more PbO, impacting the glass lattice. Optical basicity rises, suggesting improved electron transport and optical behavior. Electronegativity decreases, and electronic polarizability increases with higher PbO content, rendering the glass more electron-donating and sensitive to external electric fields.This study investigates glass mechanical properties using the Makishima–Mackenzie model. As PbO concentration rises, elastic moduli consistently decrease, signifying increased flexibility in glass structures. The mass attenuation coefficients (MAC) of the chosen glasses were evaluated in the 0.284–1.333 MeV energy range. It was found that increased PbO content leads to a corresponding MAC enhancement. The MAC values at 0.284 MeV were 0.297 and 0.349 cm2/g, while at 0.511 MeV they varied between 0.124 and 0.135 cm2/g. It was found that Glass Pb47.5 sample, which contains a higher amount of PbO compared to the other glasses, had the highest MAC at all energies. The results showed that the PbO has a notable impact on the MAC and thus on the radiation attenuation performance at lower energy. Moreover, increased glass density led to a corresponding LAC increase, which at 0.284 MeV increased from 1.269 cm−1 for Pb32.5 to 1.898 cm−1 for Pb47.5. According to the LAC results, one simple means of enhancing the glasses' radiation shielding properties is utilizing a high PbO percentage. This paper aims to illuminate silicate glasses' radiation shielding abilities. The paper will investigate the efficiency under specific conditions, like high-energy radiation. Moreover, it will explore innovative methods to enhance their shielding competence, concreting the way for a better yet effective radiation shielding approach. [ABSTRACT FROM AUTHOR]

Polyiodides present high bonding flexibility already at ambient conditions, and undergo significant pressure-induced structural deformations. Resonant Raman spectroscopy has been widely used to study I–I bonds in various polyiodides, but it carries a risk of photodecomposition due to the high visible-light absorption of iodine. In this study, tetraethylammonium (bis)diiodine triiodide (TEAI) has been investigated by resonant Raman spectroscopy up to 12.02(3) GPa. The effect of pressure on the intensities and positions of Raman bands has been evaluated and correlated with the interatomic I–I distances derived from high-pressure X-ray diffraction experiments. Pressure was shown to effectively stabilize TEAI against laser-induced photodecomposition, even after a long course of irradiation with the resonant laser light. Examination of a freshly exposed crystal surface revealed that TEAI superficially passivates with the layer of lower polyiodides, which prevents further iodine loss, and shows distinct pressure-induced behaviour. [ABSTRACT FROM AUTHOR]

Vanadium complexes have gained considerable attention as biologically active compounds. In this contribution, three previously reported dioxovanadium(V) complexes with pyridoxal semicarbazone, thiosemicarbazone, and S-methyl-iso-thiosemicarbazone ligands are theoretically examined. The intermolecular stabilization interactions within crystallographic structures were investigated by Hirshfeld surface analysis. These experimental structures were optimized at the B3LYP-D3BJ/6-311++G(d,p)(H,C,N,O,S)/def2-TZVP(V) level of theory, and crystallographic and optimized bond lengths and angles were compared. High correlation coefficients and low mean absolute errors between these two data sets proved that the selected level of theory was appropriate for the description of the system. The changes in structures and stability were examined by adding explicit solvent molecules. The Quantum Theory of Atoms in Molecules (QTAIM) was employed to analyze the intramolecular interactions with special emphasis on the effect of substituents. A good correlation between electron density/Laplacian and interatomic distance was found. Through molecular docking simulations towards Bovine Serum Albumin (BSA), the binding affinity of complexes was further investigated. The spontaneity of binding in the active position of BSA was shown. Further experimental studies on this class of compounds are advised. [ABSTRACT FROM AUTHOR]

The molecular environment in the crystal of [1,1′-bi(cyclopentane)-1,1′-diol] D-1 and [1,1′-bi(cyclohexane)-1,1′-diol] D-2 were comparatively investigated using X-ray diffraction, Hirshfeld surface analysis and two-dimensional plotting of the normalized interatomic distance. Different ways of crystallization of D-1 led to polymorphism. Studying the differences between the chemical environments of polymorphic molecules is the key for understanding the structure in the solid state. Hirshfeld analyses along with fingerprint plots revealed the differences between the two polymorphs of D-1 with anti- and syn-conformation, and the similarities between D-1 and D-2 that show the same six hydrogen bonds motif. A co-crystal DB between D-2 and a hexahydroisobenzofuran derivative was also analyzed. Fingerprint plots show a distinctive pair of spikes in the structures with cyclic hydrogen bonds as well as information about the contribution of O–H⋯O/O⋯H–O interactions, that is different for each system despite having the same number of –OH groups. Knowledge of the conformation and the intermolecular interactions is crucial to understand its role in this kind of systems and for their potential use in pharmaceutical industry, supramolecular engineering, catalysis, and design of new materials. Hirshfeld analyses along with fingerprint plots revealed the differences between two polymorphs with anti- and syn-conformation, and the similarities between compounds that show the same six hydrogen bonds motif. [ABSTRACT FROM AUTHOR]

Ca3Ru3Zn13 was synthesized from the elements in a tantalum tube in a muffle furnace. The sample was annealed to 1123 K followed by slow cooling to enhance crystal growth. Ca3Ru3Zn13 was characterized through a Guinier powder pattern. The structure was refined from single crystal X-ray diffractometer data: new type, Pbcn, a = 522.92(5), b = 1792.72(14), c = 2789.6(2) pm, wR2 = 0.0590, 3451 F2 values, 177 variables. One can describe the Ca3Ru3Zn13 structure by a stacking of closest packed layers of compositions Ca6Zn10, Ca6Zn12 and Ru6Zn15. The calcium atoms have high coordination numbers: Ca1@Zn13Ru3Ca2, Ca2@Zn15Ru4Ca, Ca3@Zn15Ru4Ca and Ca4@Zn15Ru4Ca. The shortest interatomic distances occur between the ruthenium and zinc atoms (255–273 pm). The Ru1@Zn8, Ru2@Zn10 and Ru3@Zn8 polyhedra condense via common edges to the [Ru3Zn13] substructure which hosts the calcium atoms. The zinc substructure consists of 15 crystallographically independent zinc sites with a broader range of Zn–Zn distances (255–307 pm). [ABSTRACT FROM AUTHOR]

In this work, reduced graphene oxide (rGO) is generated by an environmentally friendly electrochemical technique using an aqueous solution of 2.5 M nitric acid (HNO3), followed by thermal degradation at a temperature of 750∘C. To facilitate the exfoliation process, the electrolytic cell was equipped with a continuous supply of 54 V DC. The microstructure of the rGO sheet has been analyzed using field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). The obtained results show that rGO sheets are irregularly stacked together, have a fractured surface, and porous structure. TGA analysis depicts that the total estimated weight loss was observed to be 40% because of the removal of the oxygen functionalities and volatile gases. X-Ray diffraction (XRD) analysis was used to analyze the phase purity, crystalline nature, interatomic distance as well as crystallite size of the rGO sheet. In the Raman study, the value I D ∕ I G = 0. 4 6 2 , which compares the peak intensity of the D band to intensity of the G band, provides evidence that the structural component associated with the rGO is present. [ABSTRACT FROM AUTHOR]

Suppressing the spontaneous emission in quantum emitters ensembles (atoms) is one of the topical problems in quantum optics and quantum technology. While many approaches are based on utilizing the subradiance effect in ordered quantum emitters arrays, the ensemble configurations providing the minimal spontaneous emission rate are yet unknown. In this work, we employ the differential evolution algorithm to identify the optimal configurations of a few atomic ensembles that support quantum states with maximal radiative lifetime. We demonstrate that atoms tend to assemble mostly in quasi-regular structures with specific geometry, which strongly depends on the minimally allowed interatomic distance r min . While the discovered specific non-radiative realizations of small ensembles cannot be immediately predicted, there is particular correspondence to the non-radiative states in the atomic lattices. In particular, we have found that states inheriting their properties either from the bound states in the continuum or band edge states of infinite lattices dominate across a wide range of r min values. Additionally, we show that for small interatomic distances, the linear arrays with modulated spacing have the smallest radiative losses exponentially decreasing as the size of the ensemble increases. [ABSTRACT FROM AUTHOR]

In this paper, all molecules (1,2-ethanediol, ethanol, methoxymethanol, dimethyl ether, and dimethyl peroxide) predicted to be produced as a result of C–C, C–O, or O–O bond formation between methanol molecules induced by laser-driven shock wave were detected and identified by gas chromatography-mass spectroscopy. In this process, the ultrahigh pressure resulting from the shock wave is considered to reduce the interatomic distance between molecules to mechanically create a new chemical bond. Methoxymethanol production was further verified by infrared absorption spectroscopy of the laser-irradiated methanol concentrated by vacuum distillation. In the concentrated sample, polyoxymethylene hemiformals, which are presumably produced by the polymerization of methoxymethanol, were also found. [ABSTRACT FROM AUTHOR]

We explore the polymorphism of a weakly polar molecule, dibenzoylmethane, in which the intramolecular hydrogen-bonded enol "chelated" form is favoured. A simple geometric method on the basis of interatomic distance to visualize and count favourable connections between non-hydrogen atoms was constructed to judge the strength of intermolecular interactions in polymorphs of this kind of weakly polar molecule. The number of total favourable connections mirrored with resonance-assisted hydrogen bonds (RAHB) and aromatic interactions in DBM polymorphs increases from forms I to III, in agreement with the order of their equivalent interaction energies, proving that it is feasible for this geometric approach to be used in this weakly polar system. [ABSTRACT FROM AUTHOR]

Vanadate materials are feasible cathodes for metal–ion batteries due to their stable layered structure, abundant valence states, and high capacity. However, much uncertainty still exists about precisely modulating intercalants to facilitate ion storage. Here, V2O5 pre‐intercalated with various transition metal ions M2+ (M═Ni, Co, Mn) are developed as model materials to analyze the coupling effect between guest ions and host material. Through density functional theory simulations, it is found that M2+ interacts with V–O chain via M 3d‐O 2p covalent bonds, and extended X‐ray absorption fine structure reveals the Ni─O interatomic distance at 1.56 Å shorter than Co─O (1.60 Å) and Mn─O (1.72 Å), suggesting the M–O band type with different covalency degree can optimize VOx polyhedron and local electronic structure. Furthermore, NiVO cathode materials with the smallest layer spacing shows higher redox voltage and better rate/cycling performance for Ca2+ storage than CoVO/MnVO, elucidating that Ni has stronger tendency to attract electrons and bonds with V–O layer tightly, thus supplying a reliable ion diffusion channel for Ca2+. Through ions pre‐intercalated techniques, this work highlights both layer spacing and physicochemical properties of intercalants affect electrochemical process, which is significant for developing high‐performance vanadate cathode materials. [ABSTRACT FROM AUTHOR]

Cesium-containing thioarsenates(V) of lanthanoids with the composition Cs3Ln[AsS4]2 can be prepared for Ln = La–Nd and Sm by the oxidation of the lanthanoid metals in the presence of orpiment (As2S3), cesium sesquisulfide (Cs2S3) and elemental sulfur (S). The reaction mixtures were handled under argon atmosphere and heated in fused silica ampoules to a moderate reaction temperature of 500 °C. Single crystals of this Cs3Ln[AsS4]2 series appear as yellowish, transparent rods that are not stable to moist air and water. Their monoclinic crystal structure was determined from single-crystal X-ray diffraction data. The cesium-containing thioarsenates(V) Cs3Ln[AsS4]2 with Ln = La–Nd and Sm crystallize isotypically with Rb3Sm[PS4]2 in the non-centrosymmetric monoclinic space group P21 with Z = 2. The lattice parameters range between a = 997–1015 pm, b = 699–703 pm, c = 1192–1195 pm and β = 90.2–90.4°. There are two crystallographically different As5+ cations and one unique Ln3+ cation present, all coordinated by sulfur anions. Tetrahedral [AsS4]3− anions form two functionally different units working either as bridging units between three Ln3+ cations or as terminal ligands for Ln3+. [LnS8]13− polyhedra form ∞ 1 { [ Ln S 2 / 2 v S 6 / 1 t ] 11 − } chains propagating along [010], which are separated by Cs+ cations with coordination numbers as high as C.N. = 9, 10 and 11. Surprisingly, the eighth interatomic distance d(Ln–S3) does not follow the lanthanoid contraction, but increases with decreasing ionic radius, changing the coordination polyhedron of Ln3+ from a bicapped to a monocapped trigonal prism upon the transition from Nd to Sm, and causing a structural break in the crystal structure of this series. The results of Raman spectroscopic measurements on single crystals of Cs3La[AsS4]2 have confirmed the presence of [AsS4]3− tetrahedra as structural building blocks. [ABSTRACT FROM AUTHOR]

Knowledge about the 3-dimensional structure, orientation and interaction of chemical compounds is important in many areas of science and technology. X-ray crystallography is one of the experimental techniques capable of providing a large amount of structural information for a given compound, and it is widely used for characterisation of organic and metal-organic molecules. The method provides precise 3D coordinates of atoms inside crystals, however, it does not directly deliver information about certain chemical characteristics such as bond orders, delocalization, charges, lone electron pairs or lone electrons. These aspects of a molecular model have to be derived from crystallographic data using refined information about interatomic distances and atom types as well as employing general chemical knowledge. This publication describes a curated automatic pipeline for the derivation of chemical attributes of molecules from crystallographic models. The method is applied to build a catalogue of chemical entities in an open-access crystallographic database, the Crystallography Open Database (COD). The catalogue of such chemical entities is provided openly as a derived database. The content of this catalogue and the problems arising in the fully automated pipeline are discussed, along with the possibilities to introduce manual data curation into the process. [ABSTRACT FROM AUTHOR]

In this study, we investigate the local structure of aluminum (Al) in a comprehensive series of AlxGa1−xN epilayers, where the Al concentration spans from the dilute limit to 100%. We analyze grazing incidence Al K-edge tender x-ray absorption spectroscopy data using both linear combination fitting based on reference limit spectra and full quantitative analysis. The results indicate deviations from random cation distribution with varying signs within the explored concentration range. Additionally, we observe a reduction in cationic interatomic distances over a wide concentration range, which contrasts with some previous studies conducted at hard x-ray absorption edges. [ABSTRACT FROM AUTHOR]

Developing cost‐effective and sustainable acidic water oxidation catalysts requires significant advances in material design and in‐depth mechanism understanding for proton exchange membrane water electrolysis. Herein, we developed a single atom regulatory strategy to construct Co−Co dinuclear active sites (DASs) catalysts that atomically dispersed zirconium doped Co9S8/Co3O4 heterostructure. The X‐ray absorption fine structure elucidated the incorporation of Zr greatly facilitated the generation of Co−Co DASs layer with stretching of cobalt oxygen bond and S−Co−O heterogeneous grain boundaries interfaces, engineering attractive activity of significantly reduced overpotential of 75 mV at 10 mA cm−2, a breakthrough of 500 mA cm−2 high current density, and water splitting stability of 500 hours in acid, making it one of the best‐performing acid‐stable OER non‐noble metal materials. The optimized catalyst with interatomic Co−Co distance (ca. 2.80 Å) followed oxo‐oxo coupling mechanism that involved obvious oxygen bridges on dinuclear Co sites (1,090 cm−1), confirmed by in situ SR‐FTIR, XAFS and theoretical simulations. Furthermore, a major breakthrough of 120,000 mA g−1 high mass current density using the first reported noble metal‐free cobalt anode catalyst of Co−Co DASs/ZCC in PEM‐WE at 2.14 V was recorded. [ABSTRACT FROM AUTHOR]

Developing cost‐effective and sustainable acidic water oxidation catalysts requires significant advances in material design and in‐depth mechanism understanding for proton exchange membrane water electrolysis. Herein, we developed a single atom regulatory strategy to construct Co−Co dinuclear active sites (DASs) catalysts that atomically dispersed zirconium doped Co9S8/Co3O4 heterostructure. The X‐ray absorption fine structure elucidated the incorporation of Zr greatly facilitated the generation of Co−Co DASs layer with stretching of cobalt oxygen bond and S−Co−O heterogeneous grain boundaries interfaces, engineering attractive activity of significantly reduced overpotential of 75 mV at 10 mA cm−2, a breakthrough of 500 mA cm−2 high current density, and water splitting stability of 500 hours in acid, making it one of the best‐performing acid‐stable OER non‐noble metal materials. The optimized catalyst with interatomic Co−Co distance (ca. 2.80 Å) followed oxo‐oxo coupling mechanism that involved obvious oxygen bridges on dinuclear Co sites (1,090 cm−1), confirmed by in situ SR‐FTIR, XAFS and theoretical simulations. Furthermore, a major breakthrough of 120,000 mA g−1 high mass current density using the first reported noble metal‐free cobalt anode catalyst of Co−Co DASs/ZCC in PEM‐WE at 2.14 V was recorded. [ABSTRACT FROM AUTHOR]

1,5-Diaryl-3-Oxo-1,4-Pentadiene derivatives are intriguing organic compounds with a unique structure featuring a pentadiene core, aryl groups, and a ketone group. This study investigates the influence of fluorine atoms on the conformational features of these derivatives in deuterated chloroform (CDCl3) solution. Through nuclear magnetic resonance (NMR) spectroscopy and quantum chemical calculations, we discerned variations in interatomic distances and established predominant conformer proportions. The findings suggest that the non-fluorinated entity exhibits a uniform distribution across various conformer groups. The introduction of a fluorine atom induces substantial alterations, resulting in the predominance of a specific conformer group. This structural insight may hold the key to their diverse anticancer activities, previously reported in the literature. [ABSTRACT FROM AUTHOR]

The molecular environments in the crystal of two dibenzoylnaphthalene derivatives, having similar molecular formulas with a difference of only one substituent, that is, a 2-hydroxy group and 2-ethoxy group, were comparatively investigated with respect to the types of weak interactions, using an X-ray crystal structural study reinforced by Hirshfeld surface analysis and two-dimensional plotting of the normalised interatomic distance crossing the molecular surface. The general X-ray crystal structural analysis determined effective non-covalent bonding intra/intermolecular interactions to be the governing interactions for molecular packing based short interatomic distances. The minute spatial structure around respective interactions demonstrates the characteristics of non-covalent bonding interatomic interactions. The general X-ray crystal structural analysis further revealed the relationship between the entire crystalline symmetricity and the fashion of the interactions. Hirshfeld surface analysis revealed the location of the short contacts on the molecular surface. Two-dimensional plotting exhibited the contribution of the interacting atomic pairs covering the molecular surfaces as the geometrical distribution of the effective intermolecular non-covalent bonding interactions. The differences in the determined packing features and proximity of the two compounds were rationally interpreted according to the strength categorisation of the non-covalent bonding interactions especially in relation to the proportional/disproportional distribution of the molecular contact index. The comparison illustrated that the superior intermolecular interaction concentrates on the short interatomic distances and strain at the specified region of the molecular aggregate, resulting in adequate flexibility of the extroverted sides to achieve highly symmetrical interactions. Ethoxy–hydroxy diaroylnaphthalene compound forms cyclic classical hydrogen bond-based dimeric aggregate bearing four C–H‧‧‧O non-classical hydrogen bonds in the core region and four effective π‧‧‧π stackings around the extroverted zone, whereas ethoxy–ethoxy homologous compound shows π‧‧‧π stacking based dimeric aggregate having four C–H‧‧‧O non-classical hydrogen bonds around the extroverted zone. [ABSTRACT FROM AUTHOR]

Starting from a particle system with short-range interactions, we derive a continuum model for the bending, torsion, and brittle fracture of inextensible rods moving in three-dimensional space. As the number of particles tends to infinity, it is assumed that the rod's thickness is of the same order as the interatomic distance. For this reason, discrete terms and energy contributions from the ultrathin rod's lateral surface appear in the limiting functional. Fracture energy in the Γ -limit is expressed by an implicit cell formula, which covers different modes of fracture, including (complete) cracks, folds, and torsional cracks. In special cases, the cell formula can be significantly simplified—we illustrate this by the example of a full crack and also show that the energy of a mere fold is strictly lower for a class of models. Our approach applies e.g. to atomistic systems with Lennard–Jones-type potentials and is motivated by the research of ceramic nanowires. [ABSTRACT FROM AUTHOR]

Rare earth elements (REE) in calcium apatite have been widely described in the literature. Based on the investigations of minerals and their synthetic analogs, the mechanism of substitution of REE3+ for Ca2+ and their structural positions are well established. Although the presence of REE in natural pyromorphite has been reported, the structural response of substitution of REE3+ for Pb2+ is not established. A better understanding of REE-rich Pb-apatite may facilitate the potential use of this mineral in industrial processes. Two La-doped pyromorphite analogs [Pb5(PO4)3Cl] and two control pyromorphite analogs (with the absence of La) were synthesized from aqueous solutions at 25 °C. Na+ and K+ were used as charge-compensating ions to facilitate the incorporation of trivalent REE cations (La3+ + Na+ ↔ 2Pb2+ and La3+ + K+ ↔ 2Pb2+). Microprobe analysis, scanning electron microscopy, and Raman spectroscopy were used to confirm the purity of obtained phases. High-precision crystal structure refinements (R1 = 0.0140–0.0225) of all four compounds were performed from single-crystal X-ray diffraction data. The La content varied from 0.12(1) to 0.19(1) atoms per formula unit with the counter ions of K+ and Na+, respectively. Both substituting ions were accommodated at the Pb1 site only. By comparing the La-doped pyromorphite analogs with their control samples, it was possible to detect small changes in bond distances and polyhedral volumes caused by the La substitution. Variations in individual and mean interatomic distances reflected the cumulative effect of both the amount of substitution and ionic radii of substituting ions (La3+, Na+, and K+). [ABSTRACT FROM AUTHOR]

The Sutton–Chen potential was used to simulate the process of solidification of Ni nanoparticles at temperatures ranging from 1000 to 100 K in the cooling process. The number of atoms per particle ranged from 500 to 4000. The results show an expected increase in solidification temperature with size. Analysis of the first-neighbour interatomic distance as a function of temperature showed exponential behaviour up to the phase transition. A reduction in the interatomic distance was observed at small sizes below the established lattice parameter. Characterization of the surface as a function of the number of first neighbours allowed interpretation and quantification of the surface planes as a function of particle size at low temperatures. [ABSTRACT FROM AUTHOR]

Accurate potential energy curves (PECs) are determined for the twenty-two electronic states of LiRb. In contrast to previous studies, the applied approach relies on the first principle calculations involving correlation among all electrons. The current methodology is founded on the multireference coupled cluster (CC) scheme constructed within the Fock space (FS) formalism, specifically for the (2,0) sector. The FS methodology is established within the framework of the intermediate Hamiltonian formalism and offers an intruder-free, efficient computational scheme. This method has a distinctive feature that, when applied to the doubly ionized system, provides the characteristics of the neutral case. This proves especially beneficial when investigating PECs in situations where a closed-shell molecule dissociates into open-shell fragments, yet its double positive ion forms closed-shell species. In every instance, we successfully computed continuous PECs spanning the entire range of interatomic distances, from the equilibrium to the dissociation limit. Moreover, the spectroscopic characteristic of various electronic states is presented, including relativistic effects. Relativistic corrections included at the third-order Douglas-Kroll level have a non-negligible effect on the accuracy of the determined spectroscopic constants. [ABSTRACT FROM AUTHOR]

The quasi-atomic orbital (QUAO) bonding analysis is used to study intramolecular hydrogen bonding (IMHB) in salicylic acid and an intermediate that is crucial to the synthesis of aspirin. The bonding analysis rigorously explores IMHB through directly accessing information that is intrinsic to the molecular wave function, thereby bypassing the need for intrinsically biased methods. The variables that affect the strength of IMHB are determined using kinetic bond orders, QUAO populations, and QUAO hybridizations. Important properties include both the interatomic distance between hydrogen and oxygen participating in the IMHB and the hybridization on the oxygen. The bonding analysis further shows that each intramolecular hydrogen bond is a four-electron three-center bond. The bonding analysis is used to understand how aromatic reactivity changes due to the effect of functional groups on the aromatic ring. [ABSTRACT FROM AUTHOR]

We report an experimental and theoretical study on the shift of the hyperfine splitting frequency of ground-state Li atoms in noble gases, He, Ne, Ar, and Xe. The frequency shift is due to the change in the electron-spin density at the Li nuclei induced by collisions to the noble-gas atoms. The electron density is calculated along the interatomic distance in a pseudopotential and a dispersion potential. Based on the measured and the calculated frequency shifts, we find the importance of attractive force in collisions to helium as well as heavy noble-gas atoms. Taking advantage of the simple energy structure of the Li atom, we obtain the s wave scattering length for free electrons on noble-gas atoms by using the hyperfine splitting frequency as a precise measure. [ABSTRACT FROM AUTHOR]

In-K-edge x-ray absorption fine structure (EXAFS), x-ray photoelectron, and Raman spectroscopy results are combined for a comprehensive study of InxGa1−xN layers with energy gaps extending over nearly the whole visible spectrum. The In–N and In–(In,Ga) distances determined by EXAFS are used for the derivation of the In–N bond ionicity as well as for the phonon frequency dependence of the LO and B 1 2 modes, assessed by Raman, and the N 1s, In 3d5/2, Ga 3s, and Ga 2p1/2 electron binding energies on those distances. Phonon confinement due to perturbation of the periodic potential caused by the alloying is also quantified. [ABSTRACT FROM AUTHOR]

We examine and compare the local stress autocorrelation in the inherent states of a fragile and a strong glass: the Kob–Andersen (KA) binary mixture and the Beest–Kramer–Santen model of silica. For both systems, local (domain-averaged) stress fluctuations asymptotically reach the normal inverse-volume decay in the large domain limit; accordingly, the real-space stress autocorrelation presents long-range power law tails. However, in the case of silica, local stress fluctuations display a high degree of hyperuniformity, i.e., their asymptotic (normal) decay is disproportionately smaller than their bond level amplitude. This property causes the asymptotic power law tails of the real-space stress autocorrelation to be swamped, up to very large distances (several nanometers), by an intermediate oscillatory-exponential decay regime. Similar contributions exist in the KA stress autocorrelation, but they never can be considered as dominating the power law decay and fully disappear when stress is coarse-grained beyond one interatomic distance. Our observations document that the relevance of power-law stress correlation may constitute a key discriminating feature between strong and fragile glasses. Meanwhile, they highlight that the notion of local stress in atomistic systems involves by necessity a choice of observation (coarse-graining) scale, the relevant value of which depends, in principle, on both the model and the phenomenon studied. [ABSTRACT FROM AUTHOR]

Remote epitaxy is a recently discovered type of epitaxy, wherein single-crystalline thin films can be grown on graphene-coated substrates following the crystallinity of the substrate via remote interaction through graphene. Although remote epitaxy provides a pathway to form freestanding membranes by controlled exfoliation of grown film at the graphene interface, implementing remote epitaxy is not straightforward because atomically precise control of interface is required. Here, we unveil the role of the graphene–substrate interface on the remote epitaxy of GaAs by investigating the interface at the atomic scale. By comparing remote epitaxy on wet-transferred and dry-transferred graphene, we show that interfacial oxide layer formed at the graphene–substrate interface hinders remote interaction through graphene when wet-transferred graphene is employed, which is confirmed by an increase of interatomic distance through graphene and also by the formation of polycrystalline films on graphene. On the other hand, when dry-transferred graphene is employed, the interface is free of native oxide, and single-crystalline remote epitaxial films are formed on graphene, with the interatomic distance between the epilayer and the substrate matching with the theoretically predicted value. The first atomic layer of the grown film on graphene is vertically aligned with the top layer of the substrate with these atoms having different polarities, substantiating the remote interaction of adatoms with the substrate through graphene. These results directly show the impact of interface properties formed by different graphene transfer methods on remote epitaxy. [ABSTRACT FROM AUTHOR]

It has been hypothesized that the variation of the critical currents in Nb/Al–AlO x /Nb junctions is due to, among other effects, the presence of grain boundaries in the system. Motivated by this, we examine the effect of grain boundaries on the critical current of a Josephson junction. We assume that the hopping amplitudes are dependent on the interatomic distance and derive a physically realistic model of distance-dependent hopping amplitudes. We find that the presence of a grain boundary and associated disorder is responsible for a very large drop in the critical current relative to a clean system. We also find that when a tunnel barrier is present, grain boundaries cause substantial variations in the critical currents due to the disordered hoppings near the tunnel barrier. We discuss the applicability of these results to Josephson junctions presently intended for use in superconducting electronics applications. [ABSTRACT FROM AUTHOR]

The space charge layer in hematite photoelectrodes has been analyzed by means of Poisson–Boltzmann equations, the Stern model, and density functional theory, in view of its application for photoelectrochemical water oxidation. The width of the space charge layer can be smaller than ∼10 Å under experimental conditions. In this regime, a substantial part of the potential drop takes place in the Helmholtz layer, leading to important corrections to the Mott–Schottky behavior of the space charge layer capacitance. These results shed light on an unexpected regime of high photoelectrocatalytic efficiency, different from the classical picture of the electrochemical interface of a semiconducting photocatalyst, which is also amenable to direct study by quantum-mechanical atomistic simulations. Density functional theory has been used to calculate the band bending (BB) in the space charge layer in atomistic models of pristine stoichiometric and hydroxylated surfaces. These surface terminations display BBs of 0.14 and 0.49 eV, respectively, with an increasing width of the space charge layer, however still in the sub-nanometer regime. This work shows that, at high doping, the width of the space charge layer of a hematite photoelectrode can become comparable with interatomic distances. [ABSTRACT FROM AUTHOR]

Although 4Ce4YSZ has high corrosion resistance, it faces challenges concerning its sinterability and ionic conductivity. Therefore, we studied destabilization behavior caused by corrosion and oxygen vacancy ordering according to ZnO doping. Powders of (4Ce4YSZ)1−x(ZnO)x (x = 0.5, 1, 2, 4 mol%) were synthesized using the sol-gel method. With the addition of ZnO, the cubic phase increased, and secondary phases were not observed. The (111) peak showed a higher angle shift in ZnO-doped 4Ce4YSZ compared to 4Ce4YSZ, and TEM-SAED revealed a reduction in the spacing of the (011)t plane, suggesting lattice contraction due to the substitution of the smaller Zn2+ (60 Å) for Zr4+ (84 Å) in the lattice. The local atomic structure analysis was conducted using EXAFS to investigate the oxygen vacancy ordering behavior. Zr K-edge Fourier transform data revealed a decrease in the Zr-O1 peak intensity with an increasing amount of ZnO doping, indicating an increase in oxygen vacancies. The Zr-O1 peak position shifted to the right, leading to an increase in the Zr-O1 interatomic distance. In the Y K-edge Fourier transform data, the Y-O1 peak intensity did not decrease, and there was little variation in the Y-O1 interatomic distance. These results suggest that the oxygen vacancies formed due to ZnO doping are located in the neighboring oxygen shell of Zn, rather than in the neighboring oxygen shells of Y and Zr. Impedance measurements were conducted to measure the conductivity, and as the amount of ZnO doping increased, the total conductivity increased, while the activation energy decreased. The increase in oxygen vacancies by ZnO doping contributed to the enhancement of conductivity, and it is considered that these created oxygen vacancies did not interact with Zn2+ and did not form defect associations. Fluoride-based molten salts were introduced to the specimens to assess the corrosion behavior in a molten salt environment. Yttrium depletion layers (YDLs) were formed on the surfaces of all specimens due to the leaching of yttrium. However, Ce remained relatively stable at the interface according to EDS line scans, suggesting a reduction in the phase transformation (cubic, tetragonal to monoclinic) typically associated with yttrium leaching in YSZ. [ABSTRACT FROM AUTHOR]

Selenium atoms in aromatic selenocyanates are characterized by the occurrence of two σ-holes, a stronger one in the prolongation of the NC–Se bond and a weaker one in the prolongation of the Ar–Se bond. The crystal structures of several bis(selenocyanato) derivatives, prepared by a method originally developed for ortho bis-substituted derivatives, illustrate very well this difference, with a short NC–Se⋯NC ChB interaction organizing the molecules into 1D motifs with reduction ratio (RR) values in the range of 0.87–0.91 (RR is defined as the interatomic distance over the van der Waals contact), complemented with Ar–Se⋯NC ChB interactions between antiparallel chains involving the second σ-hole, with larger RR values in the range of 0.92–0.94. Comparison with benzylic selenocyanates shows that this secondary lateral interaction involving the weaker σ-hole is notably enhanced in these novel aromatic compounds. The structure of co-crystals of the para derivative (1,4-diselenocyanatobenzene) with (E)-1,2-di(4-pyridyl)ethylene (bpen) is characterized by an extremely short NC–Se⋯Nbpen distance at 2.693(2) Å, i.e. a RR value of 0.78, complemented with interaction of the second σ-hole with the π system of the double bond of bpen. [ABSTRACT FROM AUTHOR]

The Zintl phase K2BaSi4 has been synthesized from the mixture of precursors KSi and BaSi2. The crystal structure of K2BaSi4 was elucidated from X‐ray powder diffraction data: Pearson symbol oP28, space group Pbcm, a=9.4950(1), b=9.2392(1), c=9.9025(1) Å. The main building block of the crystal structure are tetrahedral anions Si44–. Analysis of chemical bonding for K2BaSi4 and its chemical analogs – molecular H4Si4 and solid state K4Si4 employing the electron localizability approach reveals the basic agreement with the Zintl model in terms of number of basins for Si−Si bonds and lone pairs at Si atoms, as well as the charge transfer direction. The populations of the bond and 'lone‐pair' basins agree with the Zintl count for molecular species and deviate strongly for the solids, in particular, while the 'lone‐pair' basins are over‐populated, the bond basins are essentially under‐populated. The topology of the calculated electron density and electron‐localizability indicator is very sensitive toward the interatomic distances and angles in the Si44− anion. [ABSTRACT FROM AUTHOR]

Cathodes are critical components of rechargeable batteries. Conventionally, the search for cathode materials relies on experimental trial-and-error and a traversing of existing computational/experimental databases. While these methods have led to the discovery of several commercially viable cathode materials, the chemical space explored so far is limited and many phases will have been overlooked, in particular, those that are metastable. We describe a computational framework for battery cathode exploration based on ab initio random structure searching (AIRSS), an approach that samples local minima on the potential energy surface to identify new crystal structures. We show that by delimiting the search space using a number of constraints, including chemically aware minimum interatomic separations, cell volumes, and space group symmetries, AIRSS can efficiently predict both thermodynamically stable and metastable cathode materials. Specifically, we investigate LiCoO2, LiFePO4, and LixCuyFz to demonstrate the efficiency of the method by rediscovering the known crystal structures of these cathode materials. The effect of parameters, such as minimum separations and symmetries, on the efficiency of the sampling is discussed in detail. The adaptation of the minimum interatomic distances on a species-pair basis, from low-energy optimized structures to efficiently capture the local coordination environment of atoms, is explored. A family of novel cathode materials based on the transition-metal oxalates is proposed. They demonstrate superb energy density, oxygen-redox stability, and lithium diffusion properties. This article serves both as an introduction to the computational framework and as a guide to battery cathode material discovery using AIRSS. [ABSTRACT FROM AUTHOR]

Accurate potential energy curves (PECs) are obtained for 20 lowest lying electronic states of the NaLi molecule. The computational scheme used here is based on the multireference coupled cluster theory formulated in the (2,0) sector of the Fock space. The latter sector provides the description of states obtained by attachment of two electrons to the reference system. This makes it possible to adopt the doubly ionized NaLi+2 molecule as a Fermi vacuum. The latter has a very concrete advantage in calculations of the PECs since it dissociates into closed shell fragments (NaLi+2 → Na+ + Li+); hence, the restricted Hartree–Fock method can be used within the whole range of interatomic distances. Computed PECs and spectroscopic constants stay very close to the experimental values (if the latter are available) with the accuracy exceeding the other theoretical approaches including those based on the effective core polarization potentials. Relativistic corrections included at the infinite-order two-component level have a non-negligible effect on the accuracy of computed excitation and dissociation energies with contributions up to 50 cm−1. [ABSTRACT FROM AUTHOR]

Tailoring the shape of Pd nanocrystals is one of the main ways to enhance catalytic activity; however, the effect of shapes and electrolyte pH on carbon monoxide oxidation (COOxid) is not highlighted enough. This article presents the controlled fabrication of Pd nanocrystals in different morphologies, including Pd nanosponge via the ice-cooling reduction of the Pd precursor using NaBH4 solution and Pd nanocube via ascorbic acid reduction at 25 °C. Both Pd nanosponge and Pd nanocube are self-standing and have a high surface area, uniform distribution, and clean surface. The electrocatalytic CO oxidation activity and durability of the Pd nanocube were significantly superior to those of Pd nanosponge and commercial Pd/C in only acidic (H2SO4) medium and the best among the three media, due to the multiple adsorption active sites, uniform distribution, and high surface area of the nanocube structure. However, Pd nanosponge had enhanced COOxid activity and stability in both alkaline (KOH) and neutral (NaHCO3) electrolytes than Pd nanocube and Pd/C, attributable to its low Pd-Pd interatomic distance and cleaner surface. The self-standing Pd nanosponge and Pd nanocube were more active than Pd/C in all electrolytes. Mainly, the COOxid current density of Pd nanocube in H2SO4 (5.92 mA/cm2) was nearly 3.6 times that in KOH (1.63 mA/cm2) and 10.3 times that in NaHCO3 (0.578 mA/cm2), owing to the greater charge mobility and better electrolyte–electrode interaction, as evidenced by electrochemical impedance spectroscopy (EIS) analysis. Notably, this study confirmed that acidic electrolytes and Pd nanocube are highly preferred for promoting COOxid and may open new avenues for precluding CO poisoning in alcohol-based fuel cells. [ABSTRACT FROM AUTHOR]

Analysis of the available data for several classes of homo- and heteroleptic iron-organic compounds has shown that coefficient ∇IS/aID = 0.04 mm s−1 pm−1 can be applied to describe the interrelation between the Mössbauer isomer shift and average interatomic distance between iron and the atoms of its coordination polyhedron. An additional increment was used to describe changes in the isomer shift that are not related to changes in the environment of iron or in the corresponding interatomic distances. This increment characterizes the filling of hybridized 4s4pm3dn orbitals with electrons. To calculate the increment, the value of 1.4 mm s−1 was used, which characterizes the difference between isomer shifts of iron with fully filled and half-filled hybridized shells. To compare the isomer shifts of iron compounds with ligands of different sizes, the corrections for these sizes were used. [ABSTRACT FROM AUTHOR]