Search Results (10)

The ability to fabricate bimetallic clusters with atomic precision offers promising prospects for elucidating the correlations between their structures and properties. Nevertheless, achieving precise control at the atomic level in the production of clusters, including the quantity of dopant, characteristic of ligands, charge state of precursors, and structural transformation, have remained a challenge. Herein, we report the synthesis, purification, and characterization of a new bimetallic hydride cluster, [AuCu₁₁(H){S₂P(OⁱPr)₂}₆(C≡CPh)₃] (AuCu₁₁H). The hydride position in AuCu₁₁H was determined using DFT calculations. AuCu₁₁H comprises a ligand-stabilized defective fcc Au@Cu₁₁ cuboctahedron. AuCu₁₁H is metastable and undergoes a spontaneous transformation through ligand exchange into the isostructural [AuCu₁₁(Cl){S₂P(OⁱPr)₂}₆(C≡CPh)₃] (AuCu₁₁Cl) and into the complete cuboctahedral [AuCu₁₂{S₂P(OⁱPr)₂}₆(C≡CPh)₄]⁺ (AuCu₁₂) through an increase in nuclearity. These structural transformations were tracked by NMR and mass spectrometry. Full article

Wildfires significantly influence the environmental distribution of various elements through their fire-induced input and mobilization, yet little is known about their effects on the forest floor in Siberian forests. The present study evaluated the effects of spring wildfires of various severities on the levels of major and minor (Ca, Al, Fe, S, Mg, K, Na, Mn, P, Ti, Ba, and Sr) trace and ultra-trace (B, Co, Cr, Cu, Ni, Se, V, Zn, Pb, As, La, Sn, Sc, Sb, Be, Bi, Hg, Li, Mo, and Cd) elements in the forest floors of Siberian forests. The forest floor (Oi layer) samples were collected immediately following wildfires in Scots pine (Pinus sylvestris L.), larch (Larix sibirica Ledeb.), spruce (Picea obovata Ledeb.), and birch (Betula pendula Roth) forests. Total concentrations of elements were determined using inductively coupled plasma–optical emission spectroscopy. All fires resulted in a decrease in organic matter content and an increase in mineral material content and pH values in the forest floor. The concentrations of most elements studied in a burned layer of forest floor were statistically significantly higher than in unburned precursors. Sb and Sn showed no statistically significant changes. The forest floor in the birch forest showed a higher increase in mineral material content after the fire and higher levels of most elements studied than the burned coniferous forest floors. Ca was a predominant element in both unburned and burned samples in all forests studied. Our study highlighted the role of wildfires in Siberia in enhancing the levels of geochemical elements in forest floor and the effect of forest type and fire severity on ash characteristics. The increased concentrations of elements represent a potential source of surface water contamination with toxic and eutrophying elements if wildfire ash is transported with overland flow. Full article

Orthorhombic molybdenum trioxide (α-MoO₃) is well known as a photocatalyst, adsorbent, and inhibitor during methyl orange photocatalytic degradation via TiO₂. Therefore, besides the latter, other active photocatalysts, such as AgBr, ZnO, BiOI, and Cu₂O, were assessed via the degradation of methyl orange and phenol in the presence of α-MoO₃ using UV-A- and visible-light irradiation. Even though α-MoO₃ could be used as a visible-light-driven photocatalyst, our results demonstrated that its presence in the reaction medium strongly inhibits the photocatalytic activity of TiO₂, BiOI, Cu₂O, and ZnO, while only the activity AgBr is not affected. Therefore, α-MoO₃ might be an effective and stable inhibitor for photocatalytic processes to evaluate the newly explored photocatalysts. Quenching the photocatalytic reactions can offer information about the reaction mechanism. Moreover, the absence of photocatalytic inhibition suggests that besides photocatalytic processes, parallel reactions take place. Full article

Recent Colorado, USA water law provisions allow a portion of irrigation water to be leased between agricultural and other users. Reducing consumptive use (CU) through deficit irrigation while maintaining some crop production could allow farmers to earn revenue from leasing water rights. This observational study aimed to determine if deficit irrigation of alfalfa (Medicago sativa L.) can be used to reduce CU, provide parameters for an alfalfa crop water production function (WPF), and evaluate the potential for improved farm income by leasing water. Soil water balance, evapotranspiration (ET), and dry matter yield from eight commercial fields (1.70 to 2.14 ha zones), growing subsurface drip-irrigated alfalfa, were monitored for five seasons (2018–2022) at Kersey, Colorado. Four irrigation treatments [Standard Irrigation (SI) = irrigate when soil water deficit (D) exceeds management allowed depletion (MAD); Moderate Deficit Irrigation (MDI) = 70% of SI; Severe Deficit Irrigation (SDI) = 50% of SI; and Over Irrigation (OI) = 120% of SI] were applied, with two zones per treatment. Reductions in CU ranged from 205 to 260 mm per season. The shape of the alfalfa WPF (dry biomass yield vs. ET) was concave, indicating that water use efficiency (WUE) could be optimized through deficit irrigation. The average WUE was 0.17 Mg ha⁻¹ cm⁻¹ and tended to increase with greater deficits. Deficit irrigation also increased the relative feed value. If conserved CU from deficit irrigation can be leased into a transfer water market, farmers could profit when the water lease revenue exceeds the forgone profit from alfalfa production. We found incremental profit from deficit irrigation and water leasing to be positive, assuming 2020 prices for hay ($230 bale⁻¹) and water prices above $0.50 m⁻³. Full article

Novel nanoscale probes are opening new venues for understanding unconventional electronic and magnetic functionalities driven by multiscale lattice complexity in doped high-temperature superconducting perovskites. In this work, we focus on the multiscale texture at supramolecular level of oxygen interstitial (O-i) atomic stripes in HgBa₂CuO_4+y at optimal doping for the highest superconducting critical temperature (T_C) of 94 K. We report compelling evidence for the nematic phase of oxygen interstitial O-i atomic wires with fractal-like spatial distribution over multiple scales using scanning micro- and nano-X-ray diffraction. The scale-free distribution of O-i atomic wires at optimum doping extending from the micron down to the nanoscale has been associated with the intricate filamentary network of hole-rich metallic wires in the CuO₂ plane. The observed critical opalescence provides evidence for the proximity to a critical point that controls the emergence of high-temperature superconductivity at optimum doping. Full article

In this study, we theoretically investigate the structural, electronic and magnetic properties of the Cu₂OX₂ (X = Cl, Br, I) compounds. Previous studies reported potential spin-driven ferroelectricity in Cu₂OCl₂, originating from a non-collinear magnetic phase existing below $T_N$∼70 K. However, the nature of this low-temperature magnetic phase is still under debate. Here, we focus on the calculation of J exchange couplings and enhance knowledge in the field by (i) characterizing the low-temperature magnetic order for Cu₂OCl₂ and (ii) evaluating the impact of the chemical pressure on the magnetic interactions, which leads us to consider the two new phases Cu₂OBr₂ and Cu₂OI₂. Our ab initio simulations notably demonstrate the coexistence of strong antiferromagnetic and ferromagnetic interactions, leading to spin frustration. The $T_N$ Néel temperatures were estimated on the basis of a quasi-1D AFM model using the $\mathit{ab}\mathit{initio}$J couplings. It nicely reproduces the $T_N$ value for Cu₂OCl₂ and allows us to predict an increase of $T_N$ under chemical pressure, with $T_N$ = 120 K for the dynamically stable phase Cu₂OBr₂. This investigation suggests that chemical pressure is an effective key factor to open the door of room-temperature multiferroicity. Full article

We characterized the stationary points along the nucleophilic substitution (S_N2), oxidative insertion (OI), halogen abstraction (XA), and proton transfer (PT) product channels of M⁻ + CH₃X (M = Cu, Ag, Au; X = F, Cl, Br, I) reactions using the CCSD(T)/aug-cc-pVTZ level of theory. In general, the reaction energies follow the order of PT > XA > S_N2 > OI. The OI channel that results in oxidative insertion complex [CH₃–M–X]⁻ is most exothermic, and can be formed through a front-side attack of M on the C-X bond via a high transition state OxTS or through a S_N2-mediated halogen rearrangement path via a much lower transition state invTS. The order of OxTS > invTS is inverted when changing M⁻ to Pd, a d¹⁰ metal, because the symmetry of their HOMO orbital is different. The back-side attack S_N2 pathway proceeds via typical Walden-inversion transition state that connects to pre- and post-reaction complexes. For X = Cl/Br/I, the invS_N2-TS’s are, in general, submerged. The shape of this M⁻ + CH₃X S_N2 PES is flatter as compared to that of a main-group base like F⁻ + CH₃X, whose PES has a double-well shape. When X = Br/I, a linear halogen-bonded complex [CH₃−X∙··M]⁻ can be formed as an intermediate upon the front-side attachment of M on the halogen atom X, and it either dissociates to CH₃ + MX⁻ through halogen abstraction or bends the C-X-M angle to continue the back-side S_N2 path. Natural bond orbital analysis shows a polar covalent M−X bond is formed within oxidative insertion complex [CH₃–M–X]⁻, whereas a noncovalent M–X halogen-bond interaction exists for the [CH₃–X∙··M]⁻ complex. This work explores competing channels of the M⁻ + CH₃X reaction in the gas phase and the potential energy surface is useful in understanding the dynamic behavior of the title and analogous reactions. Full article

A decanuclear silver chalcogenide cluster, [Ag₁₀(Se){Se₂P(OⁱPr)₂}₈] (2) was isolated from a hydride-encapsulated silver diisopropyl diselenophosphates, [Ag₇(H){Se₂P(OⁱPr)₂}₆], under thermal condition. The time-dependent NMR spectroscopy showed that 2 was generated at the first three hours and the hydrido silver cluster was completely consumed after thirty-six hours. This method illustrated as cluster-to-cluster transformations can be applied to prepare selenide-centered decanuclear bimetallic clusters, [Cu_xAg_10-x(Se){Se₂P(OⁱPr)₂}₈] (x = 0–7, 3), via heating [Cu_xAg_7−x(H){Se₂P(OⁱPr)₂}₆] (x = 1–6) at 60 °C. Compositions of 3 were accurately confirmed by the ESI mass spectrometry. While the crystal 2 revealed two un-identical [Ag₁₀(Se){Se₂P(OⁱPr)₂}₈] structures in the asymmetric unit, a co-crystal of [Cu₃Ag₇(Se){Se₂P(OⁱPr)₂}₈]_0.6[Cu₄Ag₆(Se){Se₂P(OⁱPr)₂}₈]_0.4 ([3a]_0.6[3b]_0.4) was eventually characterized by single-crystal X-ray diffraction. Even though compositions of 2, [3a]_0.6[3b]_0.4 and the previous published [Ag₁₀(Se){Se₂P(OEt)₂}₈] (1) are quite similar (10 metals, 1 Se²⁻, 8 ligands), their metal core arrangements are completely different. These results show that different synthetic methods by using different starting reagents can affect the structure of the resulting products, leading to polymorphism. Full article

Re sulfides were discovered in Cu–Ni–platinum-group elements (PGE) ores of the Zhelos and Tokty-Oi intrusions. These intrusions can be considered as products of the mantle superplume responsible for Rodinia’s break-up. The mineral compositions were determined in situ in polished samples. Electron microprobe analyses were mostly consistent with a general formula of (Cu,Fe,Mo,Os,Re)₅S₈, (Cu,Fe,Mo,Os,Re)₄S₇, and (Cu,Fe,Mo,Re)S₂. One of the major features of Re sulfide from the Zhelos intrusion is its high osmium content. The ΣMe/S ratio for a part of our data is consistent with that of the tarkianite. Re sulfides from the Tokty-Oi have a ΣMe/S ratio similar to those in rheniite or dzeskazganite, but differ from them by the presence of Fe and Cu and the metal-to-metal ratio. The localization of the Re sulfide within the chalcopyrite suggests its crystallization from the residual Cu-rich liquid. Full article

There is growing compelling experimental evidence that a quantum complex matter scenario made of multiple electronic components and competing quantum phases is needed to grab the key physics of high critical temperature (T_c) superconductivity in layered cuprates. While it is known that defect self-organization controls T_c, the mechanism remains an open issue. Here we focus on the theoretical prediction of the multiband electronic structure and the formation of broken Fermi surfaces generated by the self-organization of oxygen interstitials O_i atomic wires in the spacer layers in HgBa₂CuO_4+δ, La₂CuO_4+δ and La₂NiO_4+δ, by means of self-consistent Linear Muffin-Tin Orbital (LMTO) calculations. The electronic structure of a first phase of ordered O_i atomic wires and of a second glassy phase made of disordered O_i impurities have been studied through supercell calculations. We show the common features of the influence of O_i wires in the electronic structure in three types of materials. The ordering of O_i into wires leads to a separation of the electronic states between the O_i ensemble and the rest of the bulk. The wire formation first produces quantum confined localized states near the wire, which coexist with, Second, delocalized states in the Fermi surface (FS) of doped cuprates. A new scenario emerges for high T_c superconductivity, where Kitaev wires with Majorana bound states are proximity-coupled to a 2D d-wave superconductor. Full article