Remote substituent effects on homolytic Fe?C bond energies of p‐G‐C6H4CH2Fe(CO)2(η5‐C5H5) and p‐G‐C6H4(H)(CN)CFe(CO)2(η5‐C5H5) studied by Hartree–Fock and density functional theory methods

In general, both stoichiometric and catalytic reactions of organometallic complexes involve breaking and forming metal–ligand bonds. Therefore, an evaluation of the thermodynamics of such reactions requires the knowledge of metal–ligand bond energies (BDEs). The homolytic Fe? C bond dissociation energies [i.e., ΔH_homo(Fe? C)s] of 12 para‐substituted benzyldicarbonyl(η⁵‐cyclopentadienyl)iron, p‐G‐C₆H₄CH₂Fp [1,G = NO₂, CN, COMe, CO₂Me, CF₃, Br, Cl, F, H, Me, MeO, NMe₂; Fp = (η⁵‐C₅H₅)(CO)₂Fe] and 12 para‐substituted α‐cyanobenzyldicarbonyl (η⁵‐cyclopentadienyl)iron, p‐G‐PANFp [2,PAN = C₆H₄CH(CN)] were studied using Hartree–Fock (HF) and density functional theory (DFT) methods with large basis sets. The results show that BP86 and TPSSTPSS can provide the best price/performance ratio and more accurate predictions in the study of ΔH_homo(Fe? C)s. The B3LYP method satisfactorily predicts the α and remote substituent effects on ΔH_homo(Fe? C)s [ΔΔH_homo(Fe? C)s]. The fair correlations [r = 0.97 (g, 1), 0.99(g, 2)] of ΔΔH_homo(Fe? C)s of series 1 and 2 with the substituent σ constants imply that the para substituent effects on ΔH_homo(Fe? C)s originate mainly from polar effects, but those on radical stability originate from both spin delocalization and polar effects. The molecule stabilization effects (MEs) causes that not only the magnitude of ΔΔH_homo(Fe? C)s(1) varies significantly but also the direction changes from S‐pattern to O‐pattern. ΔΔH_homo(Fe? C)s(2) were found to conform to the Capto‐dative Principle. The detailed knowledge of the factors that determine the Fp? C bond strengths would greatly aid in understanding reactivity patterns in many processes. Copyright © 2010 John Wiley & Sons, Ltd.     

小球与均质自由杆的碰撞

讨论了小球与自由杆碰撞过程中所遵从的物理规律,明确了完全非弹性碰撞过程的能量特征,指出完全非弹性碰撞后两物体不一定粘在一起共同运动的事实.     

Quantum Inequality Bounds for Free Rarita-Schwinger Field in Flat Spacetime

Although quantum field theory allows the local energy density negative, it also places severe restrictions on the negative energy. One of the restrictions is the quantum energy inequality (QEI), in which the energy density is averaged over time, or space, or over space and time. By now temporal QEIs have been established for various quantum fields, but less work has been done for the spacetime quantum energy inequality. In this paper we deal with the free Rarita-Schwinger field and present a quantum inequality bound on the energy density averaged over space and time.Comparison with the QEI for the Rarita-Schwinger field shows that the lower bound is the same with the QEI. At the same time, we find the quantum inequality for the Rarita-Schwinger field is weaker than those for the scalar and Dirac fields. This fact gives further support to the conjecture that the more freedom the field has, the more easily the field displays negative energy density and the weaker the quantum inequality becomes.     

辐照电子在光纤芯处能量沉积的计算

为了用尽可能低的辐照电子能量在光纤芯处形成大的性质改变,模拟了0.1～1 MeV能量的电子辐照二氧化硅.发现每一特定能量的电子辐照二氧化硅时,在其中有个能量沉积最快的位置.计算得到0.447 4 MeV能量的电子在单模光纤中心能量沉积最快,分析发现对于这个能量的电子多数可以穿透到光纤芯处,电子能量在光纤芯处的沉积主要是由于电子能量的减小造成的.这些结果可为用电子辐照光纤制作光器件时的初始电子能量选择提供参考.     

A new energy source originating from extra dimensions

In this work the Einstein gravitational field equations and the Lichnerowicz boundary formalism in the extra dimensions are used to build up our black hole model from 6-dimensional space－time. From the internal stress－energy tensor the solutions with energy levels and semiclassical space-quantization are obtained, which combines with only one metric condition outside the defect. We show a new type of energy source, which originates from extra dimensions. A part of the energy source of quasi-stellar object (QSO) maybe come from extra dimensions in that way. The theoretical arithmetic upper limit is identical to that of the output energy of QSO.     

Reaction rate theory for supramolecular kinetics: application to protein aggregation

ABSTRACT

Probing reaction mechanisms of supramolecular processes in soft and biological matter, such as protein aggregation, is inherently challenging. This is because these processes involve multiple molecular mechanisms that are associated with the rearrangement of large numbers of weak bonds, resulting in complex free energy landscapes with many kinetic barriers. Reaction rate measurements at different temperatures can offer unprecedented insights into the underlying molecular mechanisms. However, to be able to interpret such measurements, a key challenge is to establish which properties of the complex free energy landscapes are probed by the reaction rate. Here, we present a reaction rate theory for supramolecular kinetics based on Kramers theory of diffusive reactions over multiple kinetic barriers. We find that reaction rates for protein aggregation are of the Arrhenius–Eyring type and that the associated activation energies probe only one relevant barrier along the respective free energy landscapes. We apply this advancement to interpret, in experiments and in coarse-grained computer simulations, reaction rates of amyloid aggregation in terms of molecular mechanisms and associated thermodynamic signatures. These results suggest a practical extension of the concept of rate-determining steps for complex supramolecular processes and establish a general platform for probing the underlying energy landscape using kinetic measurements.     

环戊烯分子内价轨道1a′的电子动量谱学研究

报道了环戊烯（C₅H₈）分子1a′轨道的电子动量谱，并且给出了价 轨道的电离能谱信息 .实验在非共面对称几何条件下用能量多道型电子动量谱仪完成，入射电子的能量为1200 eV 加结合能.通过Hartree-Fock 和密度泛函方法计算得到了C₅H₈分子 1a′轨道的动量谱. 对1a′轨道的电子动量谱的实验值和理论计算进行了比较，得到了该轨道的极强度（pole s trength）的信息.     

一些静电场能量公式的适用范围

讨论并给出了一些静电场能量公式的适用范围,指出明确公式的适用范围是运用这些公式的前提．     

水平梯度表面能材料表面上的滴状凝结换热系数

本文在均质表面的单个球缺形液滴换热模型和液滴通用尺度分布规律的基础上,结合梯度表面能材料表面的液滴分布和凝结换热特性,得到了一维水平梯度表面能材料表面上的滴状凝结换热计算式。在此基础上,研究了壁面过冷度、接触角梯度、工质物性等参数对梯度表面能材料表面滴状凝结换热性能的影响。结果表明:随着过冷度的增加和凝结工质汽化潜热的增大和表面张力的减小和接触角梯度的增大,平均表面凝结换热系数会增大。     

Multi-reference configuration-interaction calculations on multiply charged ions of carbon monosulfide

The potential energy curves for neutrals and multiply charged ions of carbon monosulfide are computed with highly correlated multi-reference configuration interaction wavefunctions.The correlations of inner-shell electrons with the scalar relativistic effects are included in the present computations.The spectroscopic constants,dissociation energies,ionization energies for ground and low-lying excited states together with corresponding electronic configurations of ions are obtained,and a good agreement between the present work and existing experiments is found.No theoretical evidence is found for the adiabatically stable CSq+(q>2) ions according to the present ab initio calculations.The calculated values for 1st-6th ionization energies are 11.25,32.66,64.82,106.25,159.75,and 224.64 eV,respectively.The kinetic energy release data of fragments are provided by the present work for further experimental comparisons.