On Electrostatics,Covalency, and Chemical Dashes: Physical Interactions versus Chemical Bonds

The increasing availability of real-space interaction energies between quantum atoms or fragments that provide a chemically intuitive decomposition of intrinsic bond energies into electrostatic and covalent terms [see, for instance, Chem. Eur. J. 2018 , 24, 9101] provides evidence for differences between the physicist's concept of interaction and the chemist's concept of a bond. Herein, it is argued that, for the former, all types of interactions are treated equally, whereas, for the latter, only the covalent short-range interactions have actually been used to build intuition about chemical graphs and chemical bonds. This has led to the bonding role of long-range Coulombic terms in molecular chemistry being overlooked. Simultaneously, blind consideration of electrostatic terms in chemical bonding parlance may lead to confusion. The relationship between these concepts is examined herein, and some notes of caution on how to merge them are proposed.     

The thermophysical properties of low‐temperature Pb plasma

The thermophysical properties of low‐temperature Pb plasma are calculated at temperatures 10–100 kK and densities below 0.2 of the solid‐state value. The thermodynamic values (pressure and internal energy) and transport coefficients (electrical conductivity, thermal conductivity, and thermal power) are considered. The plasma composition and thermodynamic parameters are obtained within the chemical approach, namely by means of the solution of the corresponding system of the coupled mass action law equations. Atom ionization up to +4 is taken into consideration. The electronic transport coefficients are calculated within the relaxation time approximation. The results obtained by means of the present model are compared with the available data of other models and experiments.     

Exploring Potential Energy Surfaces for Aggregation‐Induced Emission—From Solution to Crystal

Aggregation‐induced emission (AIE) is a phenomenon where non‐luminescent compounds in solution become strongly luminescent in aggregate and solid phase. It provides a fertile ground for luminescent applications that has rapidly developed in the last 15 years. In this review, we focus on the contributions of theory and computations to understanding the molecular mechanism behind it. Starting from initial models, such as restriction of intramolecular rotations (RIR), and the calculation of non‐radiative rates with Fermi's golden rule (FGR), we center on studies of the global excited‐state potential energy surfaces that have provided the basis for the restricted access to a conical intersection (RACI) model. In this model, which has been shown to apply for a diverse group of AIEgens, the lack of fluorescence in solution comes from radiationless decay at a CI in solution that is hindered in the aggregate state. We also highlight how intermolecular interactions modulate the photophysics in the aggregate phase, in terms of fluorescence quantum yield and emission color.     

Comparison of Penta and Tetra-pyridyl Cobalt-based Catalysts for Water Reduction: H2 Production Cycle,Solvent Response and Reduction Free Energy

Understanding water reduction towards H₂ generation is crucial to overcome today's renewable energy obstacles. Previous studies have shown the superior H₂ production performances of Cobalt based penta-pyridyl (CoaPPy) and tetra-pyridyl (CoaTPy) complexes in solution. We investigate H₂ production cycles of CoaPPy and CoaTPy complexes immersed in water solution by means of Ab-initio Molecular Dynamics and Density Functional Theory. We monitor dynamic properties of the systems, solvent response and structural changes occurring in the catalysts, by simulating all intermediate steps of the H₂ production cycle. Reduction free energies and reorganization energies are calculated. Our results show that, following the first electron injection, H₂ production proceeds with the singlet spin state. Following the first electron insertion, we observe a significant rearrangement of the hydrogen bonding network in the first solvation shell. The cobalt center turns out to be more accessible for the surrounding water molecules in the case of CoaTPy at all the intermediate steps, which explains its higher catalytic performance over CoaPPy. Following the first reduction reaction, a larger gain in reduction free energy is estimated for CoaTPy with respect to CoaPPy, with a difference of 0.14 eV, in line with the experiments. For the second reduction, instead, CoaPPy shows more negative reduction potential, by 0.41 eV.     

Ground-state correlation energy of counterions at a charged planar wall: Gibbs-Bogoliubov lower-bound approach

Recent simulation results imply the lowering of the ground-state correlation energy per counterion at a charged planar wall, compared with that of the 2D and 3D one-component plasma systems. Our aim is to correctly evaluate the ground-state energy of strongly-coupled counterion systems by considering a quasi-2D bound state where bound counterions are confined to a layer of molecular thickness. We use a variational approach based on the Gibbs-Bogoliubov inequality for the lower-bound free energy so that the liquid-state theory can be incorporated into the formulations. The soft mean spherical approximation demonstrates that the lowered ground-state energy can be reproduced by the obtained analytical form of a quasi-2D bound state.     

Laser control of magneto-polaron in transition metal dichalcogenides triangular quantum well

We study the dynamic of magneto-polaron condensate in monolayer two dimensional (2D) transition metal dichalcogenides (TMDs) materials of 2H types in triangular quantum well potential. Within both the quantum mechanical Schrödinger approach (QMSA) and the improved Wigner-Brillouin theory (IWBT), Landau energies levels (LELs) are derived. We have shown that the magneto-polaron condensation is enhanced in monolayer MoSe₂ compared to MoS₂, WS₂ and WSe₂. We derive various levels by increasing a magnetic field and laser parameter. We show that the quantum confinement lifts the degeneracy of the Landau levels (LLs) resulting in an anticrossing and crossing. The dephasing effect due to the quantum well potential's parameter plays an important role in the magneto-polaron energy corrections, which are also affected by the amplitude of the laser field. The system presents Stückelberg oscillations which is important for practical applications.     

On stochastic auctions in risk-averse electricity markets with uncertain supply

This paper studies risk in a stochastic auction which facilitates the integration of renewable generation in electricity markets. We model market participants who are risk averse and reflect their risk aversion through coherent risk measures. We uncover a closed form characterization of a risk-averse generator’s optimal pre-commitment behaviour for a given real-time policy, both with and without risk trading.     

Reflection of plane waves in generalized thermoelasticity of type III with nonlocal effect

The generalized thermoelasticity theory based upon the Green and Naghdi model III of thermoelasticity as well as the Eringen's nonlocal elasticity model is used to study the propagation of harmonic plane waves in a nonlocal thermoelastic medium. We found two sets of coupled longitudinal waves, which are dispersive in nature and experience attenuation. In addition to the coupled waves, there also exists one independent vertically shear-type wave, which is dispersive but experiences no attenuation. All these waves are found to be influenced by the elastic nonlocality parameter. Furthermore, the shear-type wave is found to face a critical frequency, while the coupled longitudinal waves may face critical frequencies conditionally. The problem of reflection of the thermoelastic waves at the stress-free insulated and isothermal boundary of a homogeneous, isotropic nonlocal thermoelastic half-space has also been investigated. The formulae for various reflection coefficients and their respective energy ratios are determined in various cases. For a particular material, the effects of the angular frequency and the elastic nonlocal parameter have been shown on phase speeds and the attenuation coefficients of the propagating waves. The effect of the elastic nonlocality on the reflection coefficients and the energy ratios has been observed and depicted graphically. Finally, analysis of the various results has been interpreted.