悬链线竖向集中力作用下的构形分析和张力计算

目前,悬链线在竖向集中力和均布荷载共同作用下的构形分析和受力计算的理论仍不完善。针对这一问题,通过引入悬链线的几何约束方程、力平衡方程和超越方程,建立了竖向集中力与均布荷载共同作用下的非线性方程组。采用牛顿迭代法求解方程组,得到了悬链线的构形和受力情况。为了验证理论计算的正确性,进行了算例和试验验证。结果表明,算例的计算结果与文献结论保持一致,试验测得的构形和水平张力大小与理论计算的构形和水平张力大小吻合较好。本文的理论计算可以更加简单精确地计算出悬链线在竖向集中力和均布荷载共同作用下的构形和受力情况,为实际工程提供重要的理论指导。     

基于持续同调的边坡土颗粒应力链失稳分析

采用颗粒离散元方法和持续同调理论,研究了内排土场堆叠至不同高度时的边坡稳定性。为便于研究,现采用一水平金属板向下施加压力,代替不同厚度土层的重力荷载,对边坡在竖向荷载作用下的失稳破坏过程进行了颗粒离散元模拟。研究了二维边坡土颗粒速度总矢量、边坡失稳破坏时滑移开裂面的角度以及边坡坡顶y方向的平均速度等宏观响应过程,并构建了自然堆积下边坡堆积体颗粒的法向力链无向网络模型。最后,用持续同调方法对边坡坡顶颗粒接触力链网络的拓扑特征进行分析,获得条码图,建立了岩体结构持续同调特征与失稳演化的关系。本文为研究边坡失稳拓扑识别提供了一种新方法,从而可以有效预测边坡的失稳破坏。     

Peculiar Photoinduced Electron Transfer in Porphyrin–Fullerene Akamptisomers

Porphyrin–fullerene dyads are promising candidates for organic photovoltaic devices. The electron-transfer (ET) properties of the molecular devices depend significantly on the mutual position of the donor and acceptor. Recently, a new type of molecular isomerism (akamptisomerism) has been discovered. In the present study, we explore how photoinduced ET can be modulated by passing from one akamptisomer to another. To this aim, four akamptisomers of the quinoxalinoporphyrin–[60]fullerene complex are selected for computational study. The most striking finding is that, depending on the isomer, the porphyrin unit in the dyad can act as either electron donor or electron acceptor. Thus, the stereoisomeric diversity allows one to change the direction of ET between the porphyrin and fullerene moieties. To understand the effect of akamptisomerism on the photoinduced ET processes, a detailed analysis of initial and final states involved in the ET is performed. The computed rate for charge separation is estimated to be in the region of 1–10 ns⁻¹. The formation of a long-living quinoxalinoporphyrin anion radical species is predicted.     

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.     

Semiclassical transition state theory/master equation kinetics of HO + CO: Performance evaluation

Previously, master equation (ME) simulations using semiclassical transition state theory (SCTST) and high-accuracy extrapolated ab initio thermochemistry (HEAT) predicted rate constants in excellent agreement with published experimental data over a wide range of pressure and temperatures ≳250 K, but the agreement was not as good at lower temperatures. Possible reasons for this reduced performance are investigated by (a) critically evaluating the published experimental data and by investigating; (b) three distinct ME treatments of angular momentum, including one that is exact at the zero- and infinite-pressure limits; (c) a hindered-rotor model for HOCO that implicitly includes the cis- and trans-conformers; (d) possible empirical adjustments of the thermochemistry; (e) possible empirical adjustments to an imaginary frequency controlling tunneling; (f) including or neglecting the prereaction complex PRC1; and (g) its possible bimolecular reactions. Improvements include better approximations to factors in SCTST and using the Hill and van Vleck treatment of angular momentum coupling. Evaluation of literature data does not reveal any specific shortcomings, but the stated uncertainties may be underestimated. All ME treatments give excellent fits to experimental data at T ≥ 250 K, but the discrepancy at T < 250 K persists. Note that each ME model requires individual empirical energy transfer parameters. Thermochemical adjustments were unable to match the experimental H/D kinetic isotope effects. Adjusting an imaginary frequency can achieve good fits, but the adjustments are unacceptably large. Whether PRC1 and its possible bimolecular reactions are included had little effect. We conclude that none of the adjustments is an improvement over the unadjusted theory. Note that only one set of experimental data exists in the regime of the discrepancy with theory, and data for DO + CO are scanty.     

Engineering Lithium Ions Embedded in NiFe Layered Double Hydroxide Lattices To Activate Laminated Ni2+ Sites as High-Efficiency Oxygen Evolution Reaction Catalysts

NiFe layered double hydroxides (LDHs) have been denoted as benchmark non-noble-metal electrocatalysts for the oxygen evolution reaction (OER). However, for laminates of NiFe LDHs, the edge sites are active, but the basal plane is inert, leading to underutilization as catalysts for the OER. Herein, for the first time, light and electron-deficient Li ions are intercalated into the basal plane of NiFe LDHs. The results of theoretical calculations and experiments both showed that electrons would be transferred from near Ni²⁺ to the surroundings of Li⁺, resulting in electron-deficient properties of the Ni sites, which would function as “electron-hungry” sites, to enhance surface adsorption of electron-rich oxygen-containing groups, which would enhance the effective activity for the OER. As demonstrated by the catalytic performance, the Li−NiFe LDH electrodes showed an ultralow overpotential of only 298 mV at 50 mA cm⁻², which was lower than that of 347 mV for initial NiFe LDHs and lower than that of 373 mV for RuO₂. Reasonable intercalation adjustment effectively activates laminated Ni²⁺ sites and constructs the electron-deficient structure to enhance its electrocatalytic activity, which sheds light on the functional treatment of catalytic materials.     

Generation and Reactivity of a One-Electron-Oxidized Manganese(V) Imido Complex with a Tetraamido Macrocyclic Ligand

The synthesis and X-ray structure of a new manganese(V) mesitylimido complex with a tetraamido macrocyclic ligand (TAML), [Mn^V(TAML)(N-Mes)]⁻ ( 1 ), are reported. Compound 1 is oxidized by [(p-BrC₆H₄)₃N ]^+.[SbCl₆]⁻ and the resulting Mn^VI species readily undergoes H-atom transfer and nitrene transfer reactions.     

Numerical analysis of swirling turbulent droplet-laden flow and heat transfer in a sudden pipe expansion

The effect of swirling intensity on the structure and heat transfer of a turbulent gas–droplet flow after a sudden pipe expansion has been numerically simulated. Air is used as the carrier phase, and water, ethanol, and acetone are used as the dispersed phase. The Eulerian approach is applied to simulate the dynamics and heat transfer in the dispersed phase. The gas phase is described by a system of Reynolds-averaged Navier-Stokes (RANS) equations, taking into account the effect of droplets on mean transport and turbulent characteristics in the carrier phase. Gas phase turbulence is predicted using the second-moment closure. A swirling droplet-laden flow is characterized by an increase in the number of small particles on the pipe axis due to their accumulation in the zone of flow recirculation and the action of the turbulent migration (turbophoresis) force. A rapid dispersion of fine droplets over the pipe cross-section is observed without swirling. With an increase in swirling intensity, a significant reduction in the length of the separation region occurs. The swirling of a two-phase flow with liquid droplets leads to an increase in the level of turbulence for all three types of liquid droplets investigated in this work due to their intensive evaporation. It is shown that the addition of droplets leads to a significant increase in heat transfer in comparison with a single-phase swirling flow. The greatest effect of flow swirling on heat transfer intensification in a two-phase gas-droplet flow is obtained for the droplets of ethanol and water and smallest effect is for the acetone droplets.     

Butylated hydroxytoluene enediyne: access to diradical and electrophilic quinone methide intermediates

A theoretical study was carried out on the unimolecular reaction of an enediyne with a fused butylated hydroxytoluene to internally scavenge the p‐benzyne diradical sites formed after the Bergman cyclization. The calculations revealed that the conversion of the p‐benzyne diradical (2‐tert‐butyl‐4‐methyl‐5,8‐didehydro‐1‐naphthalenol) to p‐quinone methide is favored over the conversion to a phenoxy/benzene diradical 4 in an approximate 95:5 ratio. Based on this model, the Bergman cyclization leads in a bifunctional manner to intermediates for competing reactivity with intermolecular H‐atom abstraction. Copyright © 2015 John Wiley & Sons, Ltd.     

Molecular Size and Electronic Structure Combined Effects on the Electrogenerated Chemiluminescence of Sulfurated Pyrene‐Cored Dendrimers

The electrochemistry, photophysics, and electrochemically generated chemiluminescence (ECL) of a family of polysulfurated dendrimers with a pyrene core have been thoroughly investigated and complemented by theoretical calculations. The redox and luminescence properties of dendrimers are dependent on the generation number. From low to higher generation it is both easier to reduce and oxidize them and the emission efficiency increases along the family, with respect to the polysulfurated pyrene core. The analysis of such data evidences that the formation of the singlet excited state by cation–anion annihilation is an energy‐deficient process and, thus, the ECL has been justified through the triplet–triplet annihilation pathway. The study of the dynamics of the ECL emission was achieved both experimentally and theoretically by molecular mechanics and quantum chemical calculations. It has allowed rationalization of a possible mechanism and the experimental dependence of the transient ECL on the dendrimer generation. The theoretically calculated Marcus electron‐transfer rate constant compares very well with that obtained by the finite element simulation of the whole ECL mechanism. This highlights the role played by the thioether dendrons in modulating the redox and photophysical properties, responsible for the occurrence and dynamics of the electron transfer involved in the ECL. Thus, the combination of experimental and computational results allows understanding of the dendrimer size dependence of the ECL transient signal as a result of factors affecting the annihilation electron transfer.