Metal Transition Research Articles

Phase transition and metallization of semiconductor GeSe at high pressure

Over the past few decades, semiconductor materials of the group IV-VI monochalcogenides have attracted considerable interest from researchers due to their rich structural characteristics and excellent physical properties. Among them, GeS, GeSe, SnS, and SnSe crystallize in an orthorhombic structure (Pbnm) at ambient conditions. It has been reported that GeS, SnS, and SnSe transform into a higher symmetry orthorhombic structure (Cmcm) at high pressure, while the phase transformation route of GeSe at high pressure remains controversial. As an IV-VI monochalcogenide, GeSe possesses excellent application prospects and has been extensively studied in the fields of optoelectronic and thermoelectric. Here we systematically investigate the structural behavior, optical and electrical properties of GeSe at high pressure. GeSe undergoes a phase transition from thePbnmtoCmcmphase at 33.5 GPa, like isostructural GeS, SnS, and SnSe. The optical bandgap of GeSe decreases gradually as pressure increases and undergoes a semiconducting to metallic transition above 12 GPa. This study exhibits a high-pressure strategy for modulating structural behavior, optical and electrical properties of the group IV-VI monochalcogenides to expand its prospects in optoelectronic and thermoelectric properties.

Hierarchically Structured Catalysts Toward Sustainable Hydrogen Economy: Electro- and Thermo-Chemical Pathways.

Hydrogen, as an important clean energy source, plays a more and more crucial role in decarbonizing the planet and meeting the global climate challenge due to its high energy density and zero-emission. The demand for sustainable hydrogen is increasing drastically worldwide as driven by the global shift towards low-carbon energy solutions. Thermochemical catalysis process dominates hydrogen production at scale given its relatively mature technology and commercialization status, as well as the established manufacturing infrastructure. While due to its environmentally friendly nature and growing abundant sources of renewable electricity, the electrochemical path for hydrogen production is rising as a major alternative to the thermochemical means. Nevertheless, hierarchically structured catalysts and devices have gradually taken the center stage toward replacing the traditional counterparts, especially with the rapid advancement of the design and manufacture of such ordered nanostructure assemblies toward high activity, efficient mass transport, and superb stability. In this review, the latest progress of the hierarchically structured catalysts for hydrogen production have been surveyed on electro- and thermo- chemical pathways comparatively. It covers the structure designs of atomic dispersion, nanoscale surfaces and interfaces for achieving highly active and durable catalysts, components, and devices. Both electrochemical and thermochemical approaches are reviewed in terms of the vast design details, engineered benefits, and understandings of various Pt-group metal (PGM) and non-PGM based transition metal catalysts for hydrogen production. As the growing trend, brief discussions are also presented toward the high-level assembly and manufacture of complexly structured components and devices at scale in the electrochemical and thermochemical energy systems.

Spontaneous Phase Transition and Multistage Interfacial Mechanical Friction of Liquid Metals Induced CO2 Reduction at Room Temperature

AbstractExcessive emissions of carbon dioxide (CO2) have caused the greenhouse effect and environmental crisis. Therefore, the carbon reduction and negative carbon technologies are particularly important. Among these, the negative carbon technologies that convert CO2 into carbon materials or carbon‐based chemicals for reuse have attracted significant attention. However, the strong double covalent bonds make the CO2 conversion usually require harsh conditions, complex processes, and high energy consumption. Gallium‐based liquid metals (LMs) are the functional materials with both metallic and liquid properties, exhibiting a unique liquid‐phase structure and diverse surface characteristics. Herein, a strategy for reducing CO2 is proposed to carbon materials by utilizing the spontaneous phase transition and mechanical friction of liquid metals. The gallium (Ga) and indium (In) particles are mixed and exposed to CO2, the contact interface of metal particles spontaneously transforms into liquid metals. The system has multistage interfaces, including Ga/In, Ga/eGaIn, and In/eGaIn, capable of generating triboelectrification upon mechanical stimulation, leading to charge transfer. The high electric field generated by friction at the contact interface directly reduces CO2 to carbon materials at room temperature. The carbon materials cover the surface of eGaIn and can be directly stripped for used as fuel, or industrial applications.

Pressure induced semiconductor-like to metal transition and linear magnetoresistance in Cr2S2.88 single crystal.

The transition metal chalcogenide Cr2S3-x has unique properties, such as a lower antiferromagnetic transition temperature, semiconducting behavior, and thermoelectric properties. We focus on the effects of high pressure on the properties of electrical transport and structure in the single crystal Cr2S2.88. It is observed that the resistance drops abruptly by approximately two orders of magnitude and the temperature derivative of the resistance changes from negative to positive after 15.7 GPa. The Cr2S2.88 crystal has undergone transitions from a semiconductor-like phase to a metal I phase and then to another metal II phase. Simultaneously, a structural phase transition after 16.1 GPa is confirmed by synchrotron angle dispersive X-ray diffraction (AD-XRD). After the structural phase transition, the negative magnetoresistance becomes positive with increasing pressure and shows a linear relationship in the metal II phase. Electron-type carriers dominate in the semiconductor-like phase, but hole-type carriers dominate after the structural phase transition. Our work provides an example of the effective modulation of semiconductor-like properties by pressure, which is meaningful for the innovation and development of semiconductor technology.

Stacking of charge-density waves in 2H−NbSe2 bilayers

We employ electronic-structure calculations to investigate the charge-density waves and periodic lattice distortions in bilayer 2H−NbSe2. We demonstrate that the vertical stacking can give rise to a variety of patterns that may lower the symmetry of the charge-density waves exhibited separately by the two composing 1H−NbSe2 monolayers. The general tendency to a spontaneous symmetry breaking observed in the ground state and the first excited states is shown to originate from a non-negligible interlayer coupling. Simulated images for scanning tunneling microscopy as well as geometric structure factors show signatures of the different stacking orders. This may not only be useful to reinterpret past experiments on surfaces and thin films, but it may also be exploited to devise ad hoc experiments for the investigation of the stacking order in 2H−NbSe2. We anticipate that our analysis not only applies to the 2H−NbSe2, but is also relevant for thin films and bulk, whose smallest centrosymmetric component is indeed the bilayer. Finally, our results illustrate clearly that the vertical stacking is not only important for 1T structures, as exemplified by the metal-to-insulator transition observed in 1T−TaS2, but seems to be a general feature of metallic layered transition metal dichalcogenides as well. Published by the American Physical Society 2024

Effect of an AC-DC composite longitudinal magnetic field on the microstructure and mechanical properties of WAAM Al-5 %Mg alloy

To address issues of poor forming accuracy, high porosity, and inadequate mechanical properties in wire arc additive manufacturing of aluminum alloys, this study applied external direct current (DC) and alternating current (AC) composite magnetic fields (ECMF) (AC+DC) in cold metal transition wire arc additive manufacturing (CMT-WAAM) of Al-5 % Mg alloys. The aim was to enhance the quality of forming and overall mechanical properties of the deposited specimens. Optimal ECMF (AC+DC) parameters-DC 3 A, AC 1 A, and alternating frequency 100 Hz-were determined through orthogonal experiments. Results showed that ECMF (AC+DC) facilitated arc expansion and stirred the molten pool via Lorentz force generation, thereby accelerating molten flow and improving forming precision. Compared to specimens without ECMF (AC+DC), those with ECMF (AC+DC) exhibited reduced porosity (1.07 % to 0.31 %, a decrease of 71.03 %) and finer grain size in the deposited layer (84.80 ±30.5μm to 69.10±25.1μm, an 18.51 % decrease). Additionally, average microhardness increased (83.83 HV to 96.70 HV, a 15.35 % increase), transverse tensile strength improved (239.66±1.6 MPa to 263.00± 1 MPa, a 9.86 % increase), and elongation at break enhanced from 25.50±3.8 % to 27.17±0.33 %. Longitudinal tensile strength also rose (232.33±14.33 MPa to 248.33±8.33 MPa, a 6.88 % increase), with elongation at break increasing from 19.00±7.5 % to 19.40±4.2 %. Moreover, the mechanical properties' anisotropy decreased. Consequently, ECMF (AC+DC) significantly enhanced the overall properties of CMT-WAAM Al-5 % Mg alloy deposition, providing valuable insights for extending engineering applications of Al-5 % Mg alloy WAAM.

Damage-free non-mechanical transfer strategy for highly transparent, stretchable embedded metallic micromesh electrodes

Stretchable, flexible, transparent electrodes garner significant research interest as indispensable components of flexible optoelectronic devices. However, frequent mechanical transfers during processing pose a considerable challenge in preparing electrodes of scalable size with superior performance and intact structure. Herein, we present a stretchable embedded metallic micromesh (SEMM) electrode with high optoelectronic and robust mechanical properties. The SEMM electrode is fabricated via a damage-free non-mechanical transfer strategy with the assistance of a bifunctional metal transition layer that serves as both a seed layer during electrodeposition and a sacrificial layer during stripping of the electrode. Consequently, the SEMM electrode features a scalable size and an intact structure. By optimizing the electrodeposition parameters, the SEMM achieves high optical transmittance (∼83 %) and low sheet resistance (0.22 Ω sq−1), with a figure of merit reaching 8600–53 times greater than that of commercial polyethylene terephthalate-indium tin oxide (PET-ITO). Furthermore, the SEMM exhibits excellent mechanical stability, enduring up to 60 % of tensile strain and maintaining almost constant normalized resistance after 20,000 bending cycles. Based on the SEMM, a transparent film heater yields rapid response time, low operating voltage, and fast defogging capability. This non-mechanical transfer strategy offers a compelling approach for enhancing the structural integrity and scalability of stretchable embedded transparent electrodes.

New insights into sustainable in-situ fixation of heavy metals in disturbed seafloor sediments

To address the issues of plume formation and heavy metal ion release during deep-sea mining operations, this study employed multi-sourced mineral composite roasting materials (MMCCM) of varying sizes. An in-situ capping technique was applied within a simulated system to immobilize heavy metals in contaminated sediments. The results demonstrated that capping with MMCCM of different sizes significantly suppressed the upward migration of Cu, Co, and Ni from sediments into the overlying seawater following disturbance. Ion diffusion was identified as a key mechanism driving heavy metal migration. By calculating the release rates of heavy metals during both the disturbed and undisturbed phases, it was found that the application of MMCCM induced a negative diffusion of heavy metals, indicating that the MMCCM-sediment layer functioned as a "sink" for heavy metals. FTIR and XPS analysis showed that the primary mechanisms for heavy metal removal by MMCCM were electrostatic attraction and complexation-precipitation. Additionally, capping with MMCCM facilitated the transition of heavy metals from labile to stable forms within the sediments. Through comprehensive evaluation, the long-term effectiveness of the fixed effects was demonstrated as follows: large MMCCM (L@MCM) > medium MMCCM (M@MCM) > small MMCCM (S@MCM) > powder MMCCM (P@MCM). Finally, we proposed future research directions and introduced the DQSE framework for the sustainable application of MMCCM. Based on the above findings, this study provides new insights and research references for the in-situ immobilization of heavy metals and plume reduction during future deep-sea mining processes.

Size and shape dependence of hydrogen-induced phase transformation and sorption hysteresis in palladium nanoparticles

Abstract Phase transitions of metals in hydrogen environments are critically important for applications in energy storage, catalysis, and sensing. Nanostructured metallic particles can lead to faster charging and discharging kinetics, increased lifespan, and enhanced catalytic activities. However, establishing a direct causal link between nanoparticle structure and function remains challenging. In this work, we establish a computational framework to explore the atomic configuration of a metal-hydrogen (M-H) system when in equilibrium with a H environment. This approach combines Diffusive Molecular Dynamics with an iteration strategy, aiming to minimize the system's free energy and ensure uniform chemical potential across the system that matches that of the H environment. Applying this framework, we investigate H chemical potential-composition isotherms during the hydrogenation and dehydrogenation of palladium nanoparticles, ranging in size from $3.9$ nm to $15.6$ nm and featuring various shapes including cube, rhombic dodecahedron, octahedron, and sphere. Our findings reveal an abrupt phase transformation in all examined particles during both H loading and unloading processes, accompanied by a distinct hysteresis gap between absorption and desorption chemical potentials. Notably, as particle size increases, absorption chemical potential rises while desorption chemical potential declines, consequently widening the hysteresis gap across all shapes. Regarding shape effects, we observe that, at a given size, cubic particles exhibit the lowest absorption chemical potentials during H loading, whereas octahedral particles demonstrate the highest. Moreover, octahedral particles also exhibit the highest desorption chemical potentials during H unloading. These size and shape effects are elucidated by statistics of atomic volumetric strains resulting from specific facet orientations and inhomogeneous H distributions. Prior to phase transformation in absorption, a H-rich surface shell induces lattice expansion in the H-poor core, while before phase transformation in desorption, surface stress promotes lattice compression in the H-rich core. The magnitude of the volumetric strains correlates well with the size and shape dependence, underlining their pivotal role in the observed phenomena.

A public grid of radiative transfer simulations for Lyα and metal lines in idealised galactic outflows

The vast majority of star-forming galaxies are surrounded by large reservoirs of gas ejected from the interstellar medium. Ultraviolet absorption and emission lines represent powerful diagnostics to constrain the cool phase of these outflows, through resonant transitions of hydrogen and metal ions. The interpretation of these observations is often remarkably difficult as it requires detailed modelling of the propagation of the continuum and emission lines in the gas. To this aim, we present a large public grid of ≈20 000 simulated spectra that includes H I Lyα and five metal transitions associated with Mg II, C II, Si II, and Fe II which is accessible online. The spectra have been computed with the RASCAS Monte Carlo radiative transfer code for 5760 idealised spherically symmetric configurations surrounding a central point source emission, and characterised by their column density, Doppler parameter, dust opacity, wind velocity, as well as various density and velocity gradients. Designed to predict and interpret Lyα and metal line profiles, our grid exhibits a wide diversity of resonant absorption and emission features, as well as fluorescent lines. We illustrate how it can help better constrain the wind properties by performing a joint modelling of observed Lyα, C II, and Si II spectra. Using CLOUDY simulations and virial scaling relations, we also show that Lyα is expected to be a faithful tracer of the gas at T ≈ 104 − 105 K, even if the medium is highly ionised. While C II is found to probe the same range of temperatures as Lyα, other metal lines merely trace cooler phases (T ≈ 104 K). As their gas opacity strongly depends on gas temperature, incident radiation field, metallicity and dust depletion, we caution that optically thin metal lines do not necessarily originate from low H I column densities and may not accurately probe Lyman continuum leakage.

Strange Metal and Superconductor in the Two-Dimensional Yukawa-Sachdev-Ye-Kitaev Model.

The two-dimensional Yukawa-Sachdev-Ye-Kitaev (2D-YSYK) model provides a universal theory of quantum phase transitions in metals in the presence of quenched random spatial fluctuations in the local position of the quantum critical point. It has a Fermi surface coupled to a scalar field by spatially random Yukawa interactions. We present full numerical solutions of a self-consistent disorder averaged analysis of the 2D-YSYK model in both the normal and superconducting states, obtaining electronic spectral functions, frequency-dependent conductivity, and superfluid stiffness. Our results reproduce key aspects of observations in the cuprates as analyzed by Michon etal. [Nat. Commun. 14, 3033 (2023)NCAOBW2041-172310.1038/s41467-023-38762-5]. We also find a regime of increasing zero temperature superfluid stiffness with decreasing superconducting critical temperature, as is observed in bulk cuprates.

Liquid Metal-Based Elastomer Composite with Selective Switchable Adhesion to Solids.

Selective switchable adhesion has recently attracted much attention due to its wide applications in transfer printing, information transfer, and flexible electronics. However, selective adhesive materials often have a complex adhesion or preparation process, which limits their use. To overcome this problem, this study prepares a composite of liquid metal foam and polydimethylsiloxane (PDMS) with selective photocontrolled adhesion, which can directly adhere to solids at room temperature. Utilizing the photoinduced phase transition of liquid metals, solid adhesion can be regulated by changing the backing layer modulus of the adhesive layer. Since the phase transition process is gradually completed by heat transfer from the illuminated side to the backlight side that adheres to the solid, the melting area on the backlight side can be regulated by controlling the light time, which determines the adhesion regulation area. Therefore, the accuracy of the adhesion regulation can reach less than 0.9 mm without relying on the accuracy of the infrared light. Moreover, based on the selective switchable adhesion, the selective transfer of solids with different scales can be achieved at room temperature. The findings of this study may provide strategies for the simple preparation of selective adhesive materials and the improvement of control accuracy.

The importance of the vibrational entropy in the mixing stabilization for complex ceramics

AbstractThe concept of high‐entropy materials has been introduced based on the idea that multiple principal components can be mixed through the increase in configurational entropy. Implicit in this idea is that the vibrational entropy, the other component of the mixing entropy, is small compared to the configurational entropy. To explore this relationship, we examined the mixing enthalpy, configurational entropy, and vibrational entropy of two binary ceramic systems—the transition metal carbides and transition metal diborides. We computed the vibrational entropy directly using the dynamical matrices obtained from density functional theory and the quasiharmonic approximation. The mixing vibrational entropy of the mixed diborides is at least as large as the configurational entropy while it is smaller for the carbides. Utilizing the phonon density of states, we further demonstrate the origin of the high mixing vibrational entropy arises because of a large number of new low‐frequency modes that appear in the diborides. Similar modes occur in the carbides but occur at larger frequencies. These differences ultimately arise because of the structural differences where metal atoms share nearest neighbors in the diborides, while they do not in the carbides. This increased vibrational mixing entropy dramatically enhances the mixing of the diborides and demonstrates that this type of entropy cannot be neglected when considering what stabilizes mixtures and provides a new perspective on what is considered high entropy.

Modeling of the metal–insulator transition temperature in alio-valently doped VO2 through symbolic regression

The correlated semiconductor vanadium dioxide (VO2) exhibits an insulator–metal transition (IMT) near room temperature, which is of interest in various device applications. Precise IMT temperature control is crucial to determine the use cases across technologies such as thermochromic windows, actuators for robots or neuronal oscillators. Doping the cation or anion sites can modulate the IMT by several tens of degrees and control hysteresis. However, modeling the effects of control parameters (e.g., doping concentration, type of dopants) is challenging due to complex experimental procedures and limited data, hindering the use of traditional data-driven machine learning approaches. Symbolic regression (SR) can bridge this gap by identifying nonlinear expressions connecting key input parameters to target properties, even with small data sets. In this work, we develop SR models to capture the IMT trends in VO2 influenced by different dopant parameters. Using experimental data from the literature, our study reveals a dual nature of the IMT temperature with varying tungsten (W) doping concentrations. The symbolic model captures data trends and accounts for experimental variability, providing a complementary approach to first-principles calculations. Our feature-driven analysis across a broader class of dopants informs selectivity and provides qualitative insights into tuning phase transition properties valuable for neuromorphic computing and thermochromic windows.

Signature of the Kondo effect in superparamagnetic GO incorporated Cobalt substituted Ni/NiO nanoparticles

The study reports on the magnetization, magnetoresistance, and transport properties of superparamagnetic 10% Co-doped Ni/NiO (C10-NN), Graphene Oxide (GO) incorporated 10% Co-doped Ni/NiO (C10-NNG), and 15% Co-doped Ni/NiO (C15-NN) nanoparticles synthesized via a microwave-assisted sol-gel auto-combustion method. All samples show hysteresis in negative Magnetoresistance (M-R) at different temperatures. Resistivity ρ(T) versus temperature plots of samples C10-NN and C15-NN show metallic behavior with applied fields of 0, 1, 5, 8 T, and at 0 T, 1 T respectively. However, the plot of R-T of the C15-NN sample shows a significant difference at 0 T and 1 T. At 0 T for this sample, the metallic behavior is observed for temperature T > TM, with the resistivity falling abruptly at and above TM = 246 K. The resistivity decreases with increasing temperature, exhibiting metallic behavior again above TMM < 276 K. This jump at 276 K, indicating a metal-to metal transition. The Kondo effect is observed for the first time in C10-NNG sample. The upturn of resistivity ρ(T) towards low temperature in the C10-NNG sample is well described by the power series equation and Kondo term. This sample exhibits the upturn resistivity along with a metal–insulator transition above and below the Kondo temperature TK≈ 93.51(2) K at the 0 T, 1 T, 5 T, and 8 T fields.

Structural and Electronic Phase Transitions in Three Stable Tin-Sulfur Metallic Chalcogenides under High Pressure.

As a representative homologous series, tin-bearing metallic chalcogenides (SnxSy) have sparked considerable attention because of their stoichiometric compositions and structural diversities. In this work, three stable compounds, SnS, Sn2S3, and SnS2, were screened from SnxSy and a comprehensive investigation on their structural and electrical transport properties was performed up to 60.1 GPa using a diamond anvil cell (DAC) under different hydrostatic environments. Upon nonhydrostatic compression, SnS underwent the Pnma-to-Cmcm transition accompanied by metallization at 7.6 GPa, followed by the Cmcm-to-Pm3̅m transformation at 17.8 GPa. For SnS2, the pressure-induced metallization and isostructural phase transition (IPT) occurred successively at 31.2 and 46.6 GPa, respectively. As an intermediate composition, Sn2S3 first experienced an IPT at 10.8 GPa, and then, the Pnma-to-Cmcm transition concomitantly with metallization occurred at 16.9 GPa, analogous to the high-pressure structural transformation routes of SnS and SnS2. The 0.6-5.4 GPa pressure hysteresis was detectable for the phase transitions of SnxSy under quasi-hydrostatic and hydrostatic conditions owing to the influence of deviatoric stress. In comprehensive consideration of our high-pressure Raman scattering and electrical conductivity results, the systematic construction of a pressure-phase state diagram on SnxSy not only unveils its composition-structure-property relation but also advances the in-depth exploration for other IVA-VIA metallic chalcogenides.

Temperature-induced phase transition of liquid metal for shape-adaptive triboelectric nanogenerator

Flexible wearable electronics are expected to fit different parts of the human body. However, existing energy harvester and sensor still face the difficulties of adhering to complex surfaces and spontaneously fixing to the human body. In this work, a shape-adaptive triboelectric nanogenerator (SA-TENG) based on the phase transition of liquid metal (Cd-In-Sn-Pb-Bi eutectic alloy, LM) has been constructed to achieve efficient wearable energy collection and sensitivity-tunable pressure sensing. The shape-adaptive energy harvester (SA-EH) prepared by constructing hole arrays on the electrode could be directly fixed on different parts of the human body to harvest mechanical energy for driving wearable electronics. It can generate a transferred charge density of 90.5 μC/m2 and an average power density of 45.1 mW/m2. The natural oxide layer of LM suppresses the loss of liquid electrode and increases the output by 18 % with charge trapping-blocking effect. Furthermore, a sensitivity-tunable pressure sensor (ST-PS) fabricated with microstructures on the surface of SA-TENG can realize the sensitivity of over 2.48 kPa−1 as well as the ultra-wide pressure detection range from 0.42 kPa to 113.17 kPa, and the LM-based shielding layer can weaken external interference. This novel electrode design has greatly expanded the applications of TENGs in wearable electronics.

Modulation of electronic and thermal properties of boron phosphide nanotubes under electric and magnetic fields

This work theoretically investigates the thermoelectric properties of boron phosphide nanotubes (BPNTs) using the tight-binding model, Green function method, and Kubo formalism, focusing on a zigzag BPNT with indices (20, 0). The tight binding parameters obtained by matching its band structure with calculated density functional theory band structure. The study examines the effects of transverse electric fields and axial magnetic fields on various physical properties, such as band structure, density of states (DOS), heat capacity, magnetic susceptibility, and other thermoelectric properties. BPNTs consistently show semiconducting properties with a nearly 1 eV direct band gap. The electronic properties of BPNTs are significantly affected by applied electric field, which at very strong strengths can induce a semiconducting to metallic phase transition. In contrast, the magnetic field leads to the splitting of energy bands, especially around the Fermi level. The DOS also changes with the electric field, including variations in the position, intensity, and number of DOS peaks. The thermal properties and thermoelectric performance of BPNTs are temperature-dependent. Increasing of excited electrons thermal energy cause more occupation of high energy levels in the conduction bands. The electric field further enhances the thermal properties of BPNTs by modifying their electronic properties and reducing the band gap. Stronger electric fields cause a noticeable enhancement in the BPNTs thermal properties because it is increasing the concentration of excited charge carriers. This aspect is crucial for improving the thermoelectric efficiency of BPNTs, making them more competitive for practical applications.

Catalytic effect of the in-situ rhodium(III) complexes in surfactant medium on the auto-oxidation of 1,2-hydroxyphenylthiourea: A theoretical and experimental study for rhodium(III) sensing

1,2-hydroxyphenylthiourea(HPTU) undergoes auto-oxidation to form an yellow colored dimer. The process of auto-oxidation is enhanced by the presence of trace quantities of transition metal ions and transition metal complexes that act as catalysts. In the current study, catalytic potential of rhodium(III) complexes on the auto-oxidation of 1,2-hydroxyphenylthiourea(HPTU) was studied theoretically using quantum mechanical calculations and experiments were carried out using photometry and fluorometry. DFT studies inferred that [Rh(Py)6]Cl3 showed a better catalytic activity in the dimerization of HPTU. Theoretical studies were subsequently validated through experiments using photometric methods and the range of detection was determined to be 6 ng/mL–100 ng/mL. The detection limit was observed to be 2 ng/mL. Analytical parameters such as pH, reagent concentration, metal ion concentration, appropriate activators and surfactants were established.

Pseudo-proper two-dimensional electron gas formation

Abstract In spite of the interest in the two-dimensional electron gases (2DEGs) experimentally found at surfaces and interfaces, important uncertainties remain about the observed insulator–metal transitions (IMTs). Here we show how an explicit pseudo-proper coupling of carrier sources with a relevant soft mode significantly affects the transition. The analysis presented here for 2DEGs at polar interfaces is based on group theory, Landau–Ginzburg theory, and illustrated with first-principles calculations for the prototypical case of the LaAlO 3 / SrTiO 3 interface, for which such a structural transition has recently been observed. This direct coupling implies that the appearance of the soft mode is always accompanied by carriers. For sufficiently strong coupling an avalanche-like first-order IMT is predicted.