无序碳单层的电子结构及氢原子吸附的第一性原理

本研究运用第一性原理计算方法,系统地研究了无序碳单层材料不同位点的电子结构及其析氢性能.计算结果显示无序结构中的C-C键相比于石墨烯中的C-C键在26.7%的范围内有不同程度的拉伸或压缩,使得C原子电荷在-0.17～+0.16个电子范围内变化,导致部分C原子电子局域化.电子的局域化增强了C原子的化学活性,从而表现出了较强的吸附性能.我们发现H原子与C原子的键合及析氢性能与C原子间的键角相关.对于三配位的碳原子,其中三个价电子通过sp~2杂化轨道与最邻近的碳原子结合形成较强的共价键,而余下的一个p_z轨道电子可以与H原子在垂直于原子层的方向形成较弱的化学键.无序结构可以打破三个sp~2杂化轨道的对称性,进而影响p_z轨道与氢的成键.本研究在一定程度上揭示了单层无序碳材料结构-性能的构效关系,为实验上设计特定性能的无序碳功能材料提供理论指导.     

Single-crystalline layered double hydroxides with rich defects and hierarchical structure by mild reduction for enhancing the oxygen evolution reaction

The oxygen evolution reaction(OER) with sluggish reaction kinetics and large overpotential is the critical reaction in water splitting that is promising for energy storage and conversion. Layered double hydroxides(LDHs), due to their unique lamellar structure and flexibility of chemical component, are very competing material candidates for OER. Herein, the morphology structure and the electronic structure of LDHs were simultaneously tuned to improve the OER catalytic activity by mild solvothermal reduction using ethylene glycol. The increased surface area, the introduction of oxygen vacancies and the construction of hierarchical structure greatly enhanced the electro-catalytic activity of LDHs for OER. The as-prepared LDHs showed a lower over-potential as low as 276 mV at a current density of 10 mA cm~(-2), and a small Tafel slope of 40.3 mV dec~(-1) accompanied with good stability. This work provides an efficient way to the design and optimization of advanced catalysts in the future.     

A Bubble‐Dragged Catalytic Polymer Microrocket

We report the bubble dragged microrocket consisting of functionalized multilayer polymer covered asymmetrically by platinum nanoparticles. The microrocket is pushed back during bubble growth over a small step and dragged forward over a big step during bubble explosion. Each bubble explosion induced a shock wave of gas which propagates in water at ultrafast speed. The bubble dragged microrocket can move along an approximate straight line instead of a fluctuating circle which is the trajectory of a bubble‐pushed microrocket in most cases, which makes it a promising candidate for drug delivery and simulating rod‐shaped bacteria.     

Isotropic polynomial invariants of Hall tensor

The Hall tensor emerges from the study of the Hall effect, an important magnetic effect observed in electric conductors and semiconductors. The Hall tensor is third-order and three-dimensional, whose first two indices are skew-symmetric. This paper investigates the isotropic polynomial invariants of the Hall tensor by connecting it with a second-order tensor via the third-order Levi-Civita tensor. A minimal isotropic integrity basis with 10 invariants for the Hall tensor is proposed. Furthermore, it is proved that this minimal integrity basis is also an irreducible isotropic function basis of the Hall tensor.     

Bäcklund transformation,rogue wave solutions and interaction phenomena for a $$\varvec{(3+1)}$$ ( 3 + 1 ) -dimensional B-type Kadomtsev–Petviashvili–Boussinesq equation

Nonlinear Dynamics - Under investigation in this paper is the $$(3+1)$$ -dimensional B-type Kadomtsev–Petviashvili–Boussinesq (BKP–Boussinesq) equation, which can display the...     

Local trimer orbital ordering in LiNiO2 studied by quantitative convergent beam electron diffraction technique

A local trimer orbital ordering model of LiNiO₂ was studied by means of theoretical calculation and experimental measurement of electron structure factors. Based on the trimer model, the electron structure factors were calculated by using the scattering factor of non-spherical Ni³⁺ ion. From these results, it is found that the effect of local orbital ordering on the electron structure factors of several subtle reflections, such as (202) and (107), is very large. The electron structure factors of these subtle reflections were measured by quantitative convergent beam electron diffraction method. The experimentally measured electron structure factor values of these reflections indicate that the trimer orbital ordering model is more close to the true structure of LiNiO₂.     

多波长级联拉曼光纤激光器的设计

基于稳态条件下描述光纤中受激拉曼散射效应的光功率耦合方程组,提出一种新的多波长级联拉曼光纤激光器的设计算法.结合遗传算法和打靶法的优点,采取对每一代种群中少数优良个体进行几次打靶,使得种群中目标函数最优化值附近的个体加速收敛.以500 m掺磷光纤为增益介质、光纤布拉格光栅构成谐振腔的三波长(1427 nm, 1455 nm, 1480 nm)级联拉曼光纤激光器为例,采用该算法计算了其输出特性.结果表明,总输出功率与抽运功率近似成线性关系,斜率效率约51%;由于谐振腔中三个输出波长相互之间的受激拉曼散射作用产生的能量转移,使得输出的长波长斯托克斯光斜率效率大于短波长斯托克斯光斜率效率.     

Atomistic simulations of mechanical properties of graphene nanoribbons

The mechanical behavior of graphene nanoribbons (GNRs) was investigated by molecular dynamics (MD) simulations. The simulation results showed that GNRs behave nonlinear elastically under tensile loads. When the strain exceeds 18%, the stress stiffening causes an increase in the Young's modulus. The width of a GNR has slight effects on the Young modulus and fracture strength. The maximum strain at which fracture occurs can reach 30.26% with an intrinsic strength of about 0.175 TPa. The excellent flexibility is attributed to the elongation of the CC bonds and the variations of the bond angles.     

Theoretical studies on the electronic and optical properties of arene‐ versus fluoroarene‐thiophene co‐oligomer

A series of regiochemically varied and core size extension‐modulated arene‐ and fluoroarene‐thiophene co‐oligomers and the unsubstituted sexithiophene α6T were investigated theoretically to explore their electronic and optical properties. These phenylene‐thiophene oligomers show great potential for application in organic light‐emitting diodes (OLEDs), organic diode lasers, and organic thin‐film transistors (OTFTs) because of their feasible tuning of optical and electronic properties by the various structural tunings. Density functional theory (DFT) and the ab initio HF were employed to investigate the geometric and electronic structures of the oligomers in the ground state, and the singles configuration interaction (CIS) methods were used to study the lowest singlet excited state. The lowest excitation energies (E_gs), the radiative lifetime τ, and the maximal absorption/emission wavelength of the oligomers were studied within time‐dependent DFT (TDDFT). All calculations were performed using the 6‐31G(d) basis set. The results show that the HOMOs, LUMOs, energy gaps, ionization potentials (IPs), electron affinities (EAs), and reorganization energies are significantly affected by the various structural tunings in these co‐oligomers, which is important for the improvement of the hole and electron injection into OLEDs. Interestingly, the LUMO energy of 1b , 2b , and 3b is lower than that of α6T and 1a , 2a , 3a by about 0.12 ～ 0.47 eV, indicating that the fluorophenyl‐substitution has significantly improved the electron injection properties of the oligomers. Copyright © 2008 John Wiley & Sons, Ltd.