Toward universal substituent constants: Model chemistry sensitivity of descriptors from the quantum theory of atoms in molecules

The quantum theory of atoms in molecules (QTAIM) provides a theoretical foundation to determine the properties of functional groups through additive atomic contributions. Many studies have used QTAIM in their analyses with a variety of electronic structure methods, but it is unknown if the properties measured using one model chemistry, the combination of the electronic structure method and basis set, can be compared to those measured by another. Here, we evaluate the sensitivity of QTAIM functional group and bond critical point properties using six functionals and seven basis sets. High-level B2PLYPD3-BJ/aug-cc-pV5Z reference values are provided for 116 functional groups and the property sensitivity with respect to these values are evaluated based on absolute deviations and by assessing linear relationships. Functional group properties, including charges, dipoles, quadrupoles and volumes, were found to be mostly insensitive to choice of computational model chemistry. However, due to structural and topological inconsistencies, the 6-31G(d) basis set is not recommended for use. Bond critical point properties varied with choice of model chemistry, but models incorporating hybrid functionals and triple-ζ basis sets provided values suitable for use in regression studies.     

A review of silver nanoparticles in food packaging technologies: Regulation,methods, properties,migration, and future challenges

The development of antimicrobial food packaging is needed for food preservation and quality maintenance. Silver nanoparticles (AgNPs) have been widely used as an antimicrobial agent in food packaging technologies. However, the risks associated with their potential migration into foods are a major concern. This paper comprehensively reviews the use of AgNPs in food packaging technologies. The application of AgNPs in food packaging technologies has been regulated by the United States Food and Drug Administration and the European Food Safety Authority. The addition of AgNPs into food packaging can improve their barrier, mechanical, and antibacterial properties, as well as maintain the quality of foods. Migration of AgNPs from food packaging into foods is still a concern as it has implications for human health associated with their toxicity properties. A study on the toxicological properties of AgNPs released from food packaging needs to be carried out intensively to ensure their safety before being widely implemented. Moreover, comprehensive economic evaluation to implement AgNPs in food packaging is needed as such a study is missing in the literature.     

Anisotropic Electrical,Magnetic, and Thermal Properties of In3Ni2 Intermetallic Catalyst

We present the anisotropic electrical and thermal transport coefficients (electrical resistivity, magnetoresistance, thermoelectric power, thermal conductivity), the magnetic properties, the specific heat and the electronic density of states of a monocrystalline In₃Ni₂ intermetallic compound, representing a precious-metal-free (and noble-metal-free) intermetallic catalyst for the selective hydrogenation of α,β-unsaturated aldehydes. The investigated physical parameters were determined along three orthogonal crystal-symmetry directions of the trigonal structure, the twofold axis, the 3 axis and within the mirror plane. All the investigated tensorial and vectorial quantities show the same anisotropy, with the quantities being isotropic for the twofold direction and in the mirror plane, whereas there is small, though still significant anisotropy to the 3 direction. The In₃Ni₂ crystal conducts the electricity and heat somewhat less efficiently along the 3 direction than along the twofold direction and in the mirror plane, but the differences are not large, of about 20 %. In₃Ni₂ is a diamagnetic intermetallic compound, with a presumably simple Fermi surface and electrons as the majority charge carriers.     

CaNa[Cr(OH)6] – A Layered Hydroxochromate(III) with Ordered Brucite Structure and its Thermal Decomposition

Green single-crystals of the hydroxochromate(III) CaNa[Cr(OH)₆] were grown under highly alkaline hydrothermal conditions at about 200 °C. The starting materials Ca(NO₃)₂ · 6H₂O and Cr(NO₃)₃ · 9H₂O were reacted in a mixture of water and sodium hydroxide with the molar ratio of 2.8:1. CaNa[Cr(OH)₆] crystallizes in the non-centrosymmetric trigonal space group R3 with the lattice parameters a = 583.86(2) pm and c = 1428.73(6) pm [T = 100(1) K]. Characteristically, the crystals are reverse-obverse as well as inversion twins. The crystal structure is a stack of uncharged metal hydroxide layers, which can be regarded as a cation-ordered rhombohedral variant of the Mg(OH)₂ (brucite) structure type. The oxidation state of chromium(III) and its coordination by hydroxide groups was confirmed by UV/Vis and IR spectroscopy, respectively. Temperature-dependent magnetic measurements revealed paramagnetic behavior with an effective moment of 3.82 μ_B per chromium atom. The thermal decomposition of CaNa[Cr(OH)₆] takes place at about 225 °C, where the fast elimination of 1.5 equivalents of water is followed by the oxidation of chromium(III) to chromium(VI). Upon further heating to 1000 °C and 1200 °C, the intermediate decomposition products CaCrO₄ and Na₂CrO₄ transform into the oxochromates(V) Ca₅(CrO₄)₃O_0.5 and Ca₃(CrO₄)₂, respectively.     

First-principle investigation of XSrH3 (X = K and Rb) perovskite-type hydrides for hydrogen storage

Hydrogen can be utilized as an energy source; therefore, hydrogen storage has received the most appealing examination interest in recent years. The investigations of hydrogen storage applications center fundamentally around the examination of hydrogen capacity abilities of recently presented compounds. XSrH₃ (X = K and Rb) compounds have been examined by density functional theory (DFT) calculations to uncover their different characteristics, as well as hydrogen capacity properties, for the first time. Studied compounds are optimized in the cubic phase, and optimized lattice constants are obtained as 4.77 and 4.99 Å for KSrH₃ and RbSrH₃, respectively. These hydrides have shown negative values of formation enthalpies as they are stable thermodynamically. XSrH₃ might be used in hydrogen storage applications because of high gravimetric hydrogen storage densities, which are 2.33 and 1.71 wt% for KSrH₃ and RbSrH₃, respectively. Moreover, electronic properties confirm the semiconductor nature of these compounds having indirect band gaps of values 1.41 and 1.23 eV for KSrH₃ and RbSrH₃, respectively. In addition, mechanical properties from elastic constants such as Young modulus and Pugh's ratio, also have been investigated, and these compounds were found to satisfy born stability conditions. Furthermore, Pugh's ratio and Cauchy pressure show that these hydrides have a brittle nature. Furthermore, thermodynamic properties such as entropy and Debye temperature have been examined using the quasiharmonic Debye model for different temperatures and pressures.     

Ferromagnetism and structural deformation in monolayer alpha lead oxide induced by N and F doping: New insights from first principles

We study the structural, electronic, and magnetic properties of monolayer α-PbO_0.875A_0.125 (A = N, F), which are calculated using first principles. As a result, N doping induces local ferromagnetism centered at the N²⁻ site, originating from the spin-down N 2p valence states. On the other hand, F doping induces nonmagnetism and induces ab-plane deformation, where F⁻ receives one electron to its nearest-neighboring Pb^1.75+ ions. N doping redshifts the bandgap of the undoped system and transforms it to be indirect, while F doping blueshifts the bandgap through the Burstein-Moss effect. The hybridization of Pb 6p and O 2p orbitals is stronger near the A site than that of the crystal structure edge. Our result shows new insights, predicting possible experimental results for future functional device applications.     

Tin-rich Phases RE2Au3Sn6 with RE = La,Ce, Pr,Nd, Sm – Synthesis,Structure, Magnetic Properties,and 119Sn Mössbauer Spectra

The stannides RE₂Au₃Sn₆ (RE = La, Ce, Pr, Nd, Sm) were synthesized from the elements by arc-melting. Small single crystals were grown by annealing samples in sealed tantalum tubes in an induction furnace with a special annealing sequence. The polycrystalline phases were characterized through their X-ray powder diffraction pattern. The structures of Ce₂Au₃Sn₆, Pr₂Au₃Sn₆, and Nd₂Au₃Sn₆ were refined from single-crystal X-ray diffractometer data. The RE₂Au₃Sn₆ stannides crystallize with the orthorhombic La₂Zn₃Ge₆ type, space group Cmcm. The basic structural building units are Au1@Sn₄ tetrahedra and Au2@Sn₅ square pyramids. These units are condensed to layers and the structure can be described by a simple stacking of tetrahedral and pyramidal layers with the rare earth cations in between. Temperature dependent susceptibility studies indicate that all rare earth atoms are in the trivalent oxidation state, as their effective magnetic moments match the expected values of the free RE³⁺ ions. Pr₂Au₃Sn₆ and Nd₂Au₃Sn₆ exhibit antiferromagnetic ordering at T_N = 6.3(1) and 6.7(1) K. Investigations of the electrical resistivity of La₂Au₃Sn₆ and Ce₂Au₃Sn₆ confirmed that these compounds are metallic, for La₂Au₃Sn₆ a lower resistivity was observed, in line with the absence of screening unpaired electrons. ¹¹⁹Sn Mössbauer spectra for La₂Au₃Sn₆, Ce₂Au₃Sn₆, Pr₂Au₃Sn₆ and Nd₂Au₃Sn₆ show a complex superposition of three sub-spectra which can be differentiated through their distinctly different quadrupole splitting parameters. The isomer shifts (1.87 to 2.22 mm · s^–1) indicate significant s electron density at the tin nuclei.