Transition Metal Elements Research Articles

Cobalt-doped iron-based Prussian blue analogue cubes anchored to phosphorus‑nitrogen-covered BN surfaces for enhancing the flame retardancy of epoxy coatings

Prussian blue analogue (PBA) is considered to be a very promising inorganic nano-flame retardant material due to its structure enriched with transition metal elements. Here, hexachlorocyclotriphosphazene (HCCP) and p-phenylenediamine (p-PDA) were first loaded onto the boron nitride surface (BN/PCP) via a polymerization reaction to impart richer flame retardant characteristics. Then, Co-Fe-based PBA nanoparticles were homogeneously anchored on the BN/PCP surface to obtain the BN/PCP@PBA hierarchical nano-flame retardant. It is worth mentioning that this novel composite flame retardant effectively combined the superior barrier properties of BN, fire retardancy of N, P elements and the accelerated carbon conversion effect of Co-Fe/PBA. The test results showed that the loading of PCP on the BN surface could effectively improve the thermal insulation performance of EP, while Co-Fe/PBA had good catalytic carbon formation effect at high temperature. Specifically, the backside of the BN/PCP@PBA filled EP sample displayed the lowest temperature during flame attack (164.1 °C) compared to the other specimens, proving its best thermal insulation. The BN/PCP@PBA/EP obtained the maximum expansion height and expansion rate values (27.6 mm and 21.07) in the furnace chamber experiments, which are crucial for its fire resistance. In addition, BN/PCP@PBA/EP retained the highest residual char (32.6 %) and achieved the lowest smoke density rating (36.9 %), demonstrating its high carbon conversion and fume suppression. Carbon residue analysis confirmed that the char layer of BN/PCP@PBA/EP was more complete and the metal oxides were uniformly embedded in the carbon residue skeleton, which ensured good flame protection for the substrate.

Understanding the Relation Between Intrinsic Parameters of Substituents and Physical‐Chemical Properties of NVP

AbstractNASICON‐type Na3V2(PO4)3 (NVP) is regarded as an intriguing cathode material choice for sodium ion batteries (SIBs) due to its cycling stability and relatively high capacity. However, its voltage and electronic conductivity still need to be improved for larger‐scale fast‐charging applications (e.g. electric vehicles and mobile phones). In this work, we investigate the influence of Vanadium (V) substitution by other environmentally friendly, cheap, and/or high‐valent transition metal (TM) elements on the electrochemical performance of NVP. Density functional theory calculation was used to study the volume change, voltage, conductivity, and redox mechanism during charge/discharge of different compositions. It is found that a substitution of 50% of V by Mn, Mo or W ions resulting in Na3VMn(PO4)3 (NVMnP), Na3VMo(PO4)3 (NVMoP), and Na3VW(PO4)3 (NVWP) significantly alters the cathode materials’ physical and chemical properties, notably decreasing the band gap. In particular, NVMnP has lesser than 1 eV theoretical band gap and provides a higher voltage, while NVWP a much lower voltage in comparison to NVP. This means that NVMnP and NVWP can be promising cathode and anode materials respectively. This work also establishes a relation between fundamental properties of substituents (i.e. ionization energy and ionic size) and the overall performance of NVP.

Facile Mechanochemical Synthesis of Compositionally Complex Spinel‐type Oxides, (Co, Fe, Mn)3O4, (Co, Fe, Mn, Ni)3O4, and (Co, Cr, Fe, Mn, Ni)3O4

AbstractIn the current work, a simple mechanochemical route has been employed to preparatively access three spinel‐type compositionally complex ceramics, i. e., (Co, Fe, Mn)3O4, (Co, Fe, Mn, Ni)3O4, and (Co, Cr, Fe, Mn, Ni)3O4. Hydrated nitrate salts of the respective transition metal elements were mechanically ground with ammonium hydrogen carbonate. The resulting paste‐like mixture of metal hydroxides, oxyhydroxides, and carbonates was rinsed with water to remove the byproduct (NH4NO3) and converted into the respective single‐phase spinel‐type oxides via calcination. In situ X‐ray diffraction (XRD) revealed the formation of the spinel‐type structure (Fd m) already at temperatures as low as 150 °C. Typically, the calcination of the precursors at temperatures beyond 500 °C led to the formation of well‐crystallized, single‐phase spinel‐type oxides with nearly equimolar composition and highly homogeneous distribution of the transition metals within the structure. The mechanochemical synthesis route in the present study is considered to be an easy, straightforward, and scalable access to compositionally complex oxides.

Effect of yttrium doping on the properties of Nickel-Iron multiphase heterostructures at high current conditions

Transition metal selenides hold great promise for producing clean hydrogen energy from water electrolysis, but it is not clear how transition metal elements can improve the stability of catalyst performance at high current levels. This work presents the use of nickel foam (NF) as a hydrothermal selenium substrate for yttria-doped multiphase bifunctional catalysts (Y-MSex/NF; M = Ni, Fe). Under high current circumstances, the linked structure of nanosheets and nanoscale microspheres created by hydrothermal selenium enhanced the catalytic reaction area and demonstrated exceptional performance. The overpotentials of the catalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) were 350 mV and 340 mV, respectively, at a current density of 1000 mA cm−2(j1000). Moreover, stable operation in 1.0 M potassium hydroxide at a current density of 100 mA cm−2for 50 h further demonstrated the good electrocatalytic stability. Demonstrate the potential of selenides doped with the rare earth element yttrium for total water decomposition applications.

High-throughput screening of the potential alloying elements for high-strength Mg alloys based on solid-solution strengthening

Abstract 49 types of alloy atomic dopants and their effects on the doping stability and micro-mechanical behaviour of magnesium matrix were investigated using density functional theory and high throughput first-principles calculations. Geometry optimization was performed for each doping system, and the ability of atom doping into the magnesium matrix was assessed based on the doping energy and atomic radius. Results show that the transition metal elements have negative or near negative doping energy, especially for the elements with a radius that similar to Mg. The micro-mechanical properties of the doping system were evaluated by computing the fracture energy and theoretical tensile stress. Through a screening on the doping stability and strengthening effect of 49 types of alloy atoms, a set of elements (Re, Os, Ir, Tc and W, etc.) are screened out that could strengthen the magnesium matrix with a good doping stability. The high throughput screen results serve as a theoretical guide for the selection of appropriate alloy elements for designing the high-strength magnesium alloys in the regime of solid solution strengthening effects.

Coupling mechanism of trace elements and maceral in medium and high sulphur coal in the Jurassic terrestrial environment of Zhongyuan mine in the Hengshan mining area and adjacent areas

ABSTRACT Considering the urgency of resource utilization and environmental protection, the geochemistry of anomalous trace transition metal elements in coal formed in terrestrial environments has been studied using methods such as inductively coupled plasma atomic emission spectrometry analysis, electron probe micro-area analysis, sequential chemical extraction procedures, and correlation analysis. The results indicate that minerals in the coal samples included pyrite, kaolinite, quartz, dolomite, calcite, and celestite. Furthermore, compared with the average values of coals in China and the upper continental crust, the coal samples were rich in transition metal trace elements such as Ni, Cr, and Sr and were deficient in Be, Cd, Cu, Co, Ga, Mo, Sb, Tl, V, Zn, and Ti. We found that Ni preferentially occurred in the organic matter over minerals, while Cr primarily bonded with sulfide minerals and to a lesser extent with the iron-manganese oxide minerals. Sr had a low correlation with organic matter but adhered to clay minerals and celestite. Ni enrichment in coal samples was the result of terrigenous input, while the Cr enrichment was related to intrusion of magmatic hydrothermal fluids. Sr enrichment was caused by the presence of SO4 2- in the terrigenous debris and the influence of Sr-rich water underground.

Inhomogeneous Coordination in High-entropy O3-type Cathodes Enables Suppressed Slab Gliding and Durable Sodium Storage.

O3-type layered oxides are highly promising cathodes for sodium-ion batteries (SIBs), however they undergo complex phase transitions and exhibit high sensibility to air, leading to subpar cycling performance and commercial viability. In this work, we report a layered cathode material (NaNi0.29Cu0.1Mg0.05Li0.05Mn0.2Ti0.2Sn0.11O2) with a sate-of-the-art high-entropy compositional design. We unveil that such a configuration featuring inhomogeneous coordination environment of transition metal (TM) elements, can enable enhanced gliding energy (-0.38 vs -0.58 eV) of TMO2 slabs upon desodiation both theoretically and experimentally, which underlies the fundamental origin of the outstanding structural stability of HEO materials. As a consequence, the complex phase transitions (O3-O'3-P3-P'3-P3'-O3') of conventional O3-type cathode have been eliminated, and the as-obtained material demonstrates exceptional structural robustness and integrity with an ultra-long cycle life in a quasi-solid-state cell (maintaining 73.2% capacity after 1000 cycles at 2 C). Moreover, the material presents satisfactory air stability, with minimal structural and electrochemical degradation when directly exposed to the air. An Ah-scale pouch cell based on the cathode material is constructed, demonstrating a capacity retention of 83.6% after 500 cycles, signaling substantial promise for commercial applications.

First-principles calculations of self-defects on the structural, electronic, and optical properties of BaXO3 (X = Ti, Zr, and Hf) perovskite oxide materials

This study utilizes computational simulations to examine the properties of BaXO3 (X = Ti, Zr, and Hf) perovskite oxide materials with self-defects, including vacancy and interstitial. The investigation focuses on their crystal structure, electronic characteristics, and optical behavior. The results show that the pristine BaTiO3, BaZrO3, and BaHfO3 exhibit p-type semiconductor behavior with varying band gaps. The electronic properties are primarily governed by the orbitals of oxygen and transition metal elements, suggesting potential for precise control of electron transport. Introduction of self-defects enhances the magnetization, making them suitable for magnetic applications. Moreover, these materials demonstrate promising optical properties for energy conversion and storage in the visible light and ultraviolet regions. We expected that these findings offer valuable insights for further research on perovskite oxide materials and their applications, particularly regarding the influence of self-defects during the fabrication process.

A comprehensive DFT Study of the electronic structure and optical properties of Iodine-based halide double perovskites for photovoltaic applications

This study aims to explore the electronic structure, thermodynamic, mechanical stability, and optical response of Iodine-based ordered vacancy double halide perovskite compounds through the application of density functional theory. The two compounds Cs2ZrI6 and Rb2ZrI6 exhibit thermodynamic stability, with displaying particularly notable. Moreover, analysis of the calculated coefficients of elastic stiffness confirms the mechanical stability of all materials under ambient pressure conditions. By using the Density Functional Theory with Spin-Orbit Coupling (SOC), it was observed that Cs2TeI6 and Rb2TeI6 possess an indirect band gap located between the X and L high-symmetry points, this show that Cs2TeI6, Rb2ZrI6, Cs2HfI6, and Rb2HfI6 are identified as direct semiconductor compounds. Moreover, the band gap values of X2YI6 (where X = Cs, Rb, and Y = Te, Zr, and Hf) exhibit an increasing trend as we progress along the alkali and transition metal elements in the periodic table, ranging from 1.422 eV for Cs2TeI6 to 2.465 eV for Rb2TeI6. Besides, the optical behavior of the visible light show that X2YI6 compounds have a high absorption of about 70%, reflectance of 30%, and a low transmittance. Thanks to their advantageous bandgap, enduring stabilities, and effective absorption of visible light, Cs2TeI6 and Rb2TeI6 hold significant promise for a wide range of electronic and optoelectronic applications, particularly in photovoltaics.

Efficient sorbent/catalyst composites for CO2-mediated oxidative dehydrogenation of ethane via isothermal integrated CO2 capture and utilization

The isothermal integrated CO2 capture and utilization to produce ethylene (ICCU-ODHE) performances of dual functional materials (DFM) were improved by doping five transition metal elements (Fe, Co, Ni, Cu, Zn). The results show that the DFM doped with Zn exhibits excellent ICCU-ODHE performance with an ethylene yield of 35.1 %. The results based on in-situ XPS and DFT calculation show that the doping transition metal elements can reduce the energy barriers for activating ethane and CO2. It is mainly because doping transition metal elements with strong electronegativity can increase the coordinative unsaturated Cr3+ ions to adsorb more ethane molecules, meanwhile, the doping also reduces the charge density of Cr3+ and generates additional unfilled electron orbitals facilitating charge transfer to improve the CO2 and ethane activation. However, the decrease in charge density can increase the difficulty of ethylene desorption and reduce the ethylene selectivity. In addition, the cyclic regeneration experiment shows that the ICCU-ODHE performance of DFM can decrease with the increase of cycles, however, significant performance restoration is achievable after regeneration in the air at 650 °C, attributed to the limited graphitization of coke deposition on the DFM.

Enhancing HER catalyst screening of modified MXenes through DFT and machine learning integration

AbstractMXenes doped with non‐metallic and transition metal elements exhibit remarkable potential as catalysts in the hydrogen energy. Nonetheless, efficiently identifying viable materials from a vast array of candidates remains a formidable challenge. Here, we conducted density functional theory (DFT) calculations to obtain the hydrogen adsorption free energy () of 78 types of doped TiVCO2 MXene catalysts. Then we employed machine learning models to categorize the values of the 78 catalysts, resulted in an accurate model which only uses 7 readily available elemental features but has an impressive accuracy of 93.6%. Our model successfully predicting 5 TiVCO2 catalysts doped with S with superior performance, subsequently validated through DFT calculations. This classification methodology not only evaluates the range of effectively but also facilitates qualitative prediction and screening of catalysts, presenting a novel approach for catalytic systems with limited available data.

Development of Ti3SiC2 MAX phase tubular structures for solar receiver applications

Solar receiver tubes are key components of concentrating solar-thermal power (CSP) systems that harvest solar energy. For better efficiency, the Gen3 CSP receivers, which collect heat into a heat transfer fluid, require a temperature exceeding 700 °C during operation and need to perform under extreme conditions of high temperature and high thermal stress. Operators are seeking CSP designs using new high-temperature structural materials with high thermal conductivity and high creep resistance to achieve a design life of 30 years and thus help recover the plant capital cost sooner. MAX phase materials, which consist of an early transition metal element, an A-group element, and carbon or nitrogen, are expected to exhibit high creep resistance as well as high fracture toughness. In this paper, we describe fabricating both (1) dense Ti3SiC2 MAX phase disks and (2) short-length tubes using field-assisted sintering technology (FAST). First, the disk samples that we fabricated are fully dense and contain ≈90 % Ti3SiC2 MAX phase materials and ≈10 % TiC phase materials. We determined a flexure strength of 519 ± 32 MPa by conducting a four-point bending test at room temperature with rectangular bar samples of ≈100 % density. The thermal conductivity of the Ti3SiC2 MAX phase samples, measured by light-flashing analysis, decreases linearly from a value of 41 W·m−1·K−1 at room temperature to a value of 36 W·m−1·K−1 at 650 °C. A solar reflectance measurement of the Ti3SiC2 MAX phase revealed that, temperature increases from 400 to 1400 °C, thermal emittance increases from 0.39 to 0.49, while selectivity decreases from 1.8 to 1.4, respectively. Whereas the surface oxidized MAX phase samples after 100 h exposure to air at 1000 °C exhibit that of SiC.Next, we discuss fabrication of the crack-free Ti3SiC2 MAX phase tubular structures accomplished by using FAST processing in graphite bedding. A Ti3SiC2 MAX phase content of > 95 % with traceable ≈3% remaining TiC phase and ≈15 % porosity were demonstrated after high-temperature annealing. An average fracture strength of ≈250 MPa was determined with Ti3SiC2 MAX phase tubes of ≈85 % density by diametral compression testing at room temperature. Our work demonstrated that using FAST processing to produce Ti3SiC2 MAX phase tubular structures for CSP receiver applications is a viable approach.

Electron tailoring of thermal and magnetocaloric properties in Tb55TM17.5Al27.5 (TM = Fe, Co, and Ni) metallic glasses

Transition metal (TM) elements play a key role in determining properties of magnetocaloric materials. However, the effect of TM elements on the thermodynamic behavior and magnetocaloric effect (MCE) of metallic glasses (MGs) remains elusive. In this work, ternary Tb55TM17.5Al27.5 (TM = Fe, Co, and Ni) MGs without the complexities induced by high-entropy effects were designed. It is found that both the glass transition temperature (Tg) and the initial crystallization temperature (Tx) significantly increase with decreasing 3d electron number. It leads to the low values of Trg, γ, and γm for Tb55Fe17.5Al27.5, which is consistent with its poor glass forming ability (GFA) as evidenced by the obvious lattice fringes and structural order. Despite the mediocre value of magnetic entropy change (|ΔSMpk|) for Tb55Fe17.5Al27.5, its broader magnetic transition temperature of 110.4 K associated with ∼26% evident structural order yields the maximum relative cooling power (RCP) of 546.04 J kg−1 among three MGs. Moreover, a novel weighted method for evaluating 3d electron number by consideration of the concentration and species of TM elements was adopted to reveal an inverse correlation between the 3d electron number and Tg/Tx, as well as curie temperature (Tc), |ΔSMpk|, and RCP. It is found that with the decrease of the weighted 3d electron number of TM elements, the thermal stability of rare-earth-base MGs is effectively enhanced ascribed to the strong f - d orbital hybridization effect, along with the enhanced 3d - 3d exchange interaction that induces a high Tc. This work would help us more deeply understand the role of TM elements from the perspective of electronic structure, which is crucial for designing the novel MGs with a tunable MCE and GFA applied in various cryogenic refrigeration fields.

High temperature ferrimagnetic semiconductors by spin-dependent doping in high temperature antiferromagnets

To realize room temperature ferromagnetic (FM) semiconductors is still a challenge in spintronics. Many antiferromagnetic (AFM) insulators and semiconductors with high Neel temperature TN are obtained in experiments, such as LaFeO3, BiFeO3, etc. High concentrations of magnetic impurities can be doped into these AFM materials, but AFM state with very tiny net magnetic moments was obtained in experiments because the magnetic impurities were equally doped into the spin up and down sublattices of the AFM materials. Here, we propose that the effective magnetic field provided by a FM substrate could guarantee the spin-dependent doping in AFM materials, where the doped magnetic impurities prefer one sublattice of spins, and the ferrimagnetic (FIM) materials are obtained. To demonstrate this proposal, we study the Mn-doped AFM insulator LaFeO3 with FM substrate of Fe metal by the density functional theory (DFT) calculations. It is shown that the doped magnetic Mn impurities prefer to occupy one sublattice of the AFM insulator and introduce large magnetic moments in La(Fe, Mn)O3. For the AFM insulator LaFeO3 with high TN = 740 K, several FIM semiconductors with high Curie temperature TC > 300 K and the band gap less than 2 eV are obtained by DFT calculations when 1/8 or 1/4 Fe atoms in LaFeO3 are replaced by the other 3d, 4d transition metal elements. The large magneto-optical Kerr effect (MOKE) is obtained in these LaFeO3-based FIM semiconductors. In addition, the FIM semiconductors with high TC are also obtained by spin-dependent doping in some other AFM materials with high TN, including BiFeO3, SrTcO3, CaTcO3, etc. Our theoretical results propose a way to obtain high TC FIM semiconductors by spin-dependent doping in high TN AFM insulators and semiconductors.

Finding the best frequency dependent performance of 3d transition metals (Co, Ni, and Mn) substituted nano magnetite for miniaturizing device applications

Ferrite samples with enhanced magneto-dielectric properties are more essential in electromagnetic applications. Therefore, a parent composition of Fe3O4 has been modified by substituting 3d transition metal elements (Co, Ni, Mn) at a single Fe atom using the co-precipitation synthesis method. The structural properties of the synthesized Fe3O4, NiFe2O4, CoFe2O4, and MnFe2O4 samples have been evaluated from the X-ray diffraction patterns. The surface morphology and microstructures of the studied samples were studied by field emission scanning electron microscopy and the average grain size of all the studied samples varied from 60.11 to 106.03 nm. The magneto-dielectric properties were analyzed by frequency dependent permeability (μ) and permittivity (ε) measurements for the range of 100 Hz to 100 MHz. The conduction process for the synthesized ferrites has been noticed from the ac conductivity (σac). The localized relaxation mechanism for the studied ferrites has been observed from the variation of imaginary portion of the electric modulus (M") and the impedance (Z"). Moreover, the mismatch (Z/ηο) between the impedance of the antenna substrates (Z) made of the studied samples and air (ηο) has been evaluated from the permeability and permittivity. Finally, NiFe2O4 has been derived as a suitable ferrite for miniaturizing devices over a frequency range of 10 kHz-6.5 MHz.

Improved Alkaline Hydrogen Evolution Performance of Dealloying Fe75-xCoxSi12.5B12.5 Electrocatalyst.

The electrocatalytic performance of a Fe65Co10Si12.5B12.5 Fe-based compounds toward alkaline hydrogen evolution reaction (HER) is enhanced by dealloying. The dealloying process produced a large number of nanosheets on the surface of NS-Fe65Co10Si12.5B12.5, which greatly increased the specific surface area of the electrode. When the dealloying time is 3 h, the overpotential of NS-Fe65Co10Si12.5B12.5 is only 175.1 mV at 1.0 M KOH and 10 mA cm-2, while under the same conditions, the overpotential of Fe65Co10Si12.5B12.5 is 215 mV, which is reduced. In addition, dealloying treated electrodes also show better HER performance than un-dealloying treated electrodes. With the increase in Co doping amount, the overpotential of the hydrogen evolution reaction decreases, and the hydrogen evolution activity is the best when the addition amount of Co is 10%. This work not only provides a basic understanding of the relationship between surface activity and the dealloying of HER catalysts, but also paves a new way for doping transition metal elements in Fe-based electrocatalysts working in alkaline media.

The effects of refractory elements on the properties of quaternary high entropy carbides—A first-principles and experiment study

In this work, the effects of refractory transition metal elements on the properties of quaternary equimolar ratio high entropy carbides composed of ⅣB, ⅤB and ⅥB transition metals and C element were studied by first-principles calculations and experiments.The calculation results show that all 75 kinds of high entropy carbides were thermodynamically and mechanically stable and can be formed spontaneously. Among them, Hf can promote the synthesis of high entropy carbides, while Cr has the opposite effect. In addition, single phase solid solution structures can be formed for all 73 HECs except (TiZrHfCr)C and (ZrHfVCr)C. Thereafter, the mechanical properties of these 75 quaternary HECs were compared. The calculation results show that W, Mo, and Ta have a positive effect on improving the elastic modulus, fracture toughness, hardness and melting point of high entropy carbides, while Cr has the opposite effect. The calculation results of phonon spectra show that the six high entropy carbides represented by (TiHfNbTa)C, (TiVNbTa)C, (TiZrNbTa)C, (TiZrNbCr)C, (TiZrNbMo)C and (TiZrNbW)C have lattice dynamic stability. (TiHfNbTa)C, (TiVNbTa)C, (TiZrNbTa)C, (TiZrNbMo)C and (TiZrNbW)C face-centered cubic high entropy carbides were prepared by spark plasma sintering and the microstructure and properties were tested. The experimental results are basically consistent with the calculated results.

Computational Screening of Chalcogen-Terminated Inherent Multilayer MXenes and M2AX Precursors.

Sulfur-terminated single sheet (ss-)MXene was recently achieved by delamination of multilayered van der Waals bonded (vdW)-MXenes Nb2CS2 and Ta2CS2 synthesized through solid-state synthesis, rather than via the traditional way of selectively etching A-layers from the corresponding MAX phase. Inspired by this, we perform a computational screening study of vdW-MXenes M2CCh2 isotypical to Nb2CS2 and Ta2CS2, with M = Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Mo, or W and Ch = S, Se, or Te. The thermodynamic stability of each vdW-MXene M2CCh2 is assessed, and the dynamical stability of both vdW- and ss-MXene is considered through phonon dispersions. We predict seven stable vdW-MXenes, out of which four have not been reported previously, and one, V2CSe2, incorporates a new transition metal element into this family of materials. Electronic properties are presented for the vdW- and ss-forms of the stable vdW-MXenes, suggesting that the materials are either metallic, semimetallic, or semiconducting. In previous experimental reports the vdW-MXene Nb2CS2 is synthesized by manipulation of the corresponding M2AX phase Nb2SC. Therefore, we also evaluate the thermodynamic stability of the corresponding M2AX phases, identifying 15 potentially stable phases. Six of these are experimentally reported, leaving nine new M2AX phases for future experimental investigation.

A theoretical study on excited-state dynamical properties and laser cooling of zinc monohydride including spin-orbit couplings.

By means of highly accurate ab initio and dynamical calculations, we identify a suitable laser cooling candidate that contains a transition metal element, namely zinc monohydride (ZnH). The internally contracted multireference configuration interaction method is employed to compute the five lowest-lying Λ-S states of ZnH with the spin-orbit coupling effects included, and very good agreement is obtained between our calculated and experimental spectroscopic data. Our findings show that the position of crossing point of the A2Π and B2Σ+ states of ZnH is above the v' = 2 vibrational level of the A2Π state indicating that the crossings with higher electronic states will have no effect on laser cooling. Hence, we construct a feasible laser-cooling scheme for ZnH using five lasers based on the A2Π1/2 → X2Σ+ 1/2 transition, which features a large vibrational branching ratio R 00 (0.8458), a large number of scattered photons (9.8 × 103) and an extremely short radiative lifetime (64ns). The present work demonstrates the importance of electronic state crossings and spin-orbit couplings in the study of molecular laser cooling.

Cycloadditions of Diazoalkenes with P4 and tBuCP: Access to Diazaphospholes.

Diazoalkenes readily react with tert-butylphosphaalkyne (tBuCP) and white phosphorus (P4) to afford novel phosphorus heterocycles, 3H-1,2,4-diazamonophospholes and 1,2,3,4-diazadiphospholes. Both species represent rare examples of neutral heterophospholes. The mechanism of formation and the electronic structures of these formal (3+2) cycloaddition products were analyzed computationally. The new phospholes form structurally diverse coordination compounds with transition metal and main group elements. Given the growing number of stable diazoalkenes, this work offers a straightforward route to neutral aza(di-)phospholes as a new ligand class.