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.     

无水坝抽水蓄能系统高压溶气问题研究

无水坝抽水蓄能系统利用封闭容器内的高压气体构建虚拟水坝,是兼具压缩空气储能和抽水蓄能优点的新型储能系统。但该系统的封闭容器内水和气在高压状态共存有可能造成水中溶气,从而对水轮机造成汽蚀等破坏。本文采用实际气体状态方程及分子动力学模拟方法,研究了宽广的压力、温度范围下气体在水中的溶解及扩散规律,揭示了水中气体溶解量随时间和水深的变化规律。研究结果表明释能结束后保证水-气共容舱内剩余水的高度大于0.5 m时,高压溶气不会对水轮机产生危害,该结论对系统的工程应用及推广具有指导意义。     

Diffraction mode selection in planar Bragg resonators of optical and microwave wavelength ranges

Using the coupled waves approach complemented by the time-domain quasi-optical approximation, we solve a 2D diffraction problem which allows to evaluate the eigenfrequencies, quality factors and spatial structures of eigenmodes in planar Bragg resonators with a finite length and width of the corrugated area. We find the values of the Fresnel parameter determined by the geometrical dimensions of the system which allows for efficient transverse mode discrimination due to the larger diffraction losses of the modes with higher transverse numbers.     

3D打印贝壳仿生复合材料的拉伸力学行为

采用硬质和软质双组分材料,通过调控两种基体材料的装配夹角,采用光固化3D打印技术制备了不同装配方式的仿贝壳珍珠层复合材料,开展了准静态拉伸实验,结合扫描电镜观察,分析了其拉伸力学性能、断裂及能量耗散机理。研究结果表明,保持胞元边长不变,随着面内装配角度增加,仿贝壳珍珠层复合材料的强度呈线性增加趋势,断裂应变呈线性减小的趋势;随着面外装配角度增大,断裂应变呈线性减小趋势,而强度在面外装配角小于45°时呈增强趋势,超过45°时趋于稳定;面外装配角度为45°时,材料的强度达到最大值。试样在断裂前主要通过硬质材料的拔出、软/硬相界面处微裂纹的生成及微裂纹在扩展过程中的合并和偏转等方式耗散能量。     

Energy conditions of the f(T,B) gravity dark energy model with the validity of thermodynamics

In this article, the analysis of Tsallis holographic dark energy(which turns into holographic dark energy for a particular choice of positive non-additivity parameter δ) in modified f(T, B) gravity with the validity of thermodynamics and energy conditions for a homogeneous and isotropic FLRW Universe has been studied. The enlightenment of the field equation towards f(T,B)=αT~m+βB~n, made possible by the fact that the model is purely accelerating,corresponds to q=-0.54(Mamon and Das 2017 Eur. Phys.J.C 77 49). The generalized second law of thermodynamics is valid not only for the same temperature inside the horizon, but also for the apparent horizon for a change in temperature. The essential inspiration driving this article is to exhibit the applicability that the holographic dark energy achieved from standard Tsallis holographic dark energy and the components acquired from f(T, B) gravity are identical for the specific bounty of constants. The analysis of energy conditions confirms that the weak energy condition and the null energy condition are fulfilled throughout the expansion, while violation of the strong energy condition validates the accelerated expansion of the Universe.With the expansion, the model becomes a quintessence dominated model. The dominant energy condition is not observed initially when the model is filled with genuine baryonic matter,whereas it appears when the model is in the quintessence dominated era.     

Emergence of a non-Fowler-Nordheim-type behavior for a general planar tunneling barrier

In this work we investigate a generalized tunneling barrier for planar emitters at zero-temperature. We present the evidence of the emergence of a non-Fowler-Nordheim-type general behavior for the field emission current density in the case that the Fermi energy (μ) is comparable with or smaller that the decay width ($d_F$). Therefore, for some non-metals or materials that have very small Fermi energy the standard Fowler-Nordheim-type theory may require a correction. In the opposite regime, i.e., for μ much larger that $d_F$, we confirm that the conventional theory is suitable for metals.