Ultrahard magnetism from mixed-valence dilanthanide complexes with metal-metal bonding

Magnetic effects of lanthanide bonding Lanthanide coordination compounds have attracted attention for their persistent magnetic properties near liquid nitrogen temperature, well above alternative molecular magnets. Gould et al . report that introducing metal-metal bonding can enhance coercivity. Reduction of iodide-bridged terbium or dysprosium dimers resulted in a single electron bond between the metals, which enforced alignment of the other valence electrons. The resultant coercive fields exceeded 14 tesla below 50 and 60 kelvin for the terbium and dysprosium compounds, respectively. —JSY

Modulating the Frontier Orbitals of an Aluminylene for Facile Dearomatization of Inert Arenes

Lewis bases are well known to stabilize electron-deficient species. We demonstrate herein that the redox property of a monocoordinated aluminylene 1 featuring only four valence electrons for the shell of Al can be boosted by a Lewis base. The coordination of 1 with an N-heterocyclic carbene (NHC) effectively shrinks the HOMO−LUMO gap, thereby enhancing the reactivity of the ensuing acyclic mono-NHC-stabilized aluminylene 2, which is isoelectronic with singlet carbenes. Moreover, such base coordination completely reverses the predominant chemical reactivity (i.e. electrophilicity/nucleophilicity) of aluminylenes. In marked contrast to 1, 2 readily undergoes a [4+1] cycloaddition reaction with naphthalene and biphenylene at room temperature. Remarkably, the enhanced ambiphilic nature of Al in 2 also enables facile cleavage of aromatic C−C bonds of inert arenes in both intra- and intermolecular fashion affording 3 and 5. The formation of 5 represents the first example of the cleavage of aromatic C(3)−C(4) bond in biphenylene by a single atom center.

Modulating the Frontier Orbitals of an Aluminylene for Facile Dearomatization of Inert Arenes

Lewis bases are well known to stabilize electron-deficient species. We demonstrate herein that the redox property of a monocoordinated aluminylene 1 featuring only four valence electrons for the shell of Al can be boosted by a Lewis base. The coordination of 1 with an N-heterocyclic carbene (NHC) effectively shrinks the HOMO−LUMO gap, thereby enhancing the reactivity of the ensuing acyclic mono-NHC-stabilized aluminylene 2, which is isoelectronic with singlet carbenes. Moreover, such base coordination completely reverses the predominant chemical reactivity (i.e. electrophilicity/nucleophilicity) of aluminylenes. In marked contrast to 1, 2 readily undergoes a [4+1] cycloaddition reaction with naphthalene and biphenylene at room temperature. Remarkably, the enhanced ambiphilic nature of Al in 2 also enables facile cleavage of aromatic C−C bonds of inert arenes in both intra- and intermolecular fashion affording 3 and 5. The formation of 5 represents the first example of the cleavage of aromatic C(3)−C(4) bond in biphenylene by a single atom center.

Substrate Effect on Hydrogen Evolution Reaction in Two-Dimensional Mo2C Monolayers

The physical and chemical properties of atomically thin two-dimensional (2D) materials can be modified by the substrates. In this study, the substrate effect on the electrocatalytic hydrogen evolution reaction (HER) in 2D Mo2C monolayers was investigated using first principles calculations. The isolated Mo2C monolayer shows large variation in HER activity depending on hydrogen coverage: it has relatively low activity at low hydrogen coverage but high activity at high hydrogen coverage. Ag, Au, Cu, and graphene were used as substrates to study the substrate effect. While the effects of the Au and graphene substrates on the HER activity are insignificant, Ag and Cu substrates improve the HRE activity, especially at low hydrogen coverage, by modifying the valence electrons in the Mo2C layer; therefore, the HER activity of the Mo2C monolayer becomes high for any hydrogen coverage. Our results suggest that, in two-dimensional electrocatalysis, the substrate has a degree of freedom to tune the catalytic activity.

Superconductivity of twisted double bi-layer graphene in chiral model

Taking into account the sp -hybridization effect for valence electrons in carbon atoms, a very simple chiral model of graphene was suggested some years ago [1]. This model used as a special order parameter the unitary SU(2) -matrix U with the kink-like (or domain wall) structure for the description of electrons in a mono-atomic graphene sheet. However, later the new graphene physics began since studying twisted multilayer configurations revealing unconventional superconducting properties (twist-tronics) [2]. Within the scope of the chiral model these twisted configurations can be described by the so-called “product ansatz” U = U1U2 ▪ ▪ ▪ Un . As an example, the special case of twisted double bi-layer graphene (TDBG) configuration is studied and the corresponding twist angles, for which the superconductivity takes place, are found.

Gas fuel combustion and related problems

Combustion, as it is well known, is based on chemical reactions. If we look at a clear scientific definition of the term “combustion”, then combustion will be a process of rapid high-temperature oxidation, combining physical and chemical phenomena. Combustion consists of a large number of elementary redox processes leading to the redistribution of valence electrons between atoms of interacting substances.Modern theories of combustion relate flame spreading in gases to chemical chain reactions[1]. Nowadays, in a view of the wide spread of gas, understanding of a ship fuel and analysis of gas related problems of combustion are more and more critical. Gas itself is not able to ignite in a combustion chamber as a conventional fuel just because of compression and temperature rising. It requires a strong and efficient source of fire. The article is focused on analyzing igniting, flame spreading and detonation in a combustion chamber. The detonation condition was assessed in case of using gas as ships fuel.

Collision dynamics of cytosine under proton irradiation

In the framework of the time-dependent density-functional theory, applied to valence electrons, coupled non-adiabatically to molecular dynamics of ions, the collision dynamics of cytosine impacted by proton is studied. We especially focus on the effect of the collision orientations on the damage of cytosine by choosing two collision orientations taking the oxygen atom on the double bond CO as the collision site with the incident energy of proton ranging from 150 eV to 1000 eV. First, two collision dynamical processes are explored by analyzing the molecular ionization, the ionic position and the kinetic energy, the energy loss of proton and the electronic density evolution. The results show that the damage process of cytosine induced by proton impact is mainly the capture of electrons by proton, the departments of ions and groups as well as the opening of ring. It is found that the orientation has little effect on the loss of the kinetic energy of proton, which is about 21.5[Formula: see text] of the incident energy of proton. Although the scattering angle [Formula: see text] has a polynomial relationship with [Formula: see text] in both cases, it is greatly affected by the orientation. When [Formula: see text] eV, the scattering angle of proton colliding with O along the x-axis is greater than that of proton colliding with O along the y-axis. The orientation also has a great effect on the mass distribution of the fragments and the fragmentation route. When proton moves along the x-axis, the fragmentation route is that O leaves the cytosine and the rest keeps on vibration, while products are not only related to the incident kinetic energy, but also show diversity when proton moves along the y-axis.

Anion-exchange-mediated internal electric field for boosting photogenerated carrier separation and utilization

Heterojunctions modulated internal electric field (IEF) usually result in suboptimal efficiencies in carrier separation and utilization because of the narrow IEF distribution and long migration paths of photocarriers. In this work, we report distinctive bismuth oxyhydroxide compound nanorods (denoted as BOH NRs) featuring surface-exposed open channels and a simple chemical composition; by simply modifying the bulk anion layers to overcome the limitations of heterojunctions, the bulk IEF could be readily modulated. Benefiting from the unique crystal structure and the localization of valence electrons, the bulk IEF intensity increases with the atomic number of introduced halide anions. Therefore, A low exchange ratio (~10%) with halide anions (I–, Br–, Cl–) gives rise to a prominent elevation in carrier separation efficiency and better photocatalytic performance for benzylamine coupling oxidation. Here, our work offers new insights into the design and optimization of semiconductor photocatalysts.

Theoretical investigations on correlations between elastic behavior of Al-based alloys and their electronic structures

In this work, using the first-principles method, the alloying stability, electronic structure, and elastic properties of Al-based intermetallics were investigated. It was found that these alloys have a strong alloying ability and structural stability due to the negative formation energies and the cohesive energies. The valence bonds of these intermetallic compounds are attributed to the valence electrons of Cu 3δ states for AlCu3, Cu 3δ and Zr 4δ states for AlCu2Zr, and Al 3s, Zr 5s and 4δ states for AlZr3, respectively. Furthermore, the correlation between elastic properties of these intermetallic compounds and their electronic structures was revealed. The results show that structural parameters and elastic properties such as bulk modulus, shear modulus, Young’s modulus, Poisson’s ratio and anisotropy agreed well with experimental results.