How deeply are core electrons perturbed when valence electrons are spin polarized? The case study of transition metal compounds

The ferromagnetic and antiferromagnetic wave functions of the KMnF₃ perovskite have been evaluated quantum-mechanically by using an all electron approach and, for comparison, pseudopotentials on the transition metal and the fluorine ions. It is shown that the different number of α and β electrons in the d shell of Mn perturbs the inner shells, with shifts between the α and β eigenvalues that can be as large as 6 eV for the 3s level, and is far from negligible also for the 2s and 2p states. The valence electrons of F are polarized by the majority spin electrons of Mn, and in turn, spin polarize their 1s electrons. When a pseudopotential is used, such a spin polarization of the core functions of Mn and F can obviously not take place. The importance of such a spin polarization can be appreciated by comparing (i) the spin density at the Mn and F nuclear position, and then the Fermi contact constant, a crucial quantity for the hyperfine coupling, and (ii) the ferromagnetic–antiferromagnetic energy difference, when obtained with an all electron or a pseudopotential scheme, and exploring how the latter varies with pressure. This difference is as large as 50% of the all electron datum, and is mainly due to the rigid treatment of the F ion core. The effect of five different functionals on the core spin polarization is documented.     

Mobility of Li+, Na+, and Cs+ cations in Nafion membrane,as studied by NMR techniques

The local mobility and diffusion of Li⁺, Na⁺, and Cs⁺ cations in Nafion 117 membrane were explored by ⁷Li, ²³Na, and ¹³³Cs spin relaxation and pulsed field gradient NMR techniques. It was shown that the macroscopic mass transfer of cations is controlled by ion motion near sulfonate groups. Lithium and sodium cations, whose hydrated energy is higher than the water hydrogen bond energy, are moving together with water molecules, but cesium cations possessing a low hydrated energy are jumping directly between the neighboring sulfonate groups.     

有机物同分异构体的学习进阶研究

分析了高中生学习同分异构体的思维过程,建构碳架异构、位置异构、官能团类型异构、信息加工推理的四维度五水平模型。合理设计学习进阶,系统发展高中同分异构体思维水平,得到三学段五层级十二进阶设计。系统规划进阶,精准评价思维,建议使用结构模型和思维导图进行教学,发展学生同分异构体的思维水平,培养学生模型认知的核心素养。     

化学师范生手持技术接受度与TPACK的相关性研究

以技术接受度模型(Technology Acceptance Model, TAM)与TPACK(Technological Pedagogical Content Knowledge,整合信息技术、教学法、学科内容的知识结构)理论为基础,以手持技术为技术接受度模型与TPACK中的技术对象,利用结构方程模型调查研究H大学化学师范生的手持技术接受度与TPACK的相关性。研究发现：(1)化学师范生对手持技术的行为意愿、感知易用性、主观规范正向影响TPACK的发展;(2)化学师范生对手持技术的感知有用性与自我效能正向影响行为意愿,并能通过行为意愿间接影响TPACK的发展。最后,基于研究结果,提出发挥示范引领作用、重视优质资源的整合应用等提升化学师范生手持技术TPACK的4条建议。     

真实情境下问题解决的主题式教学设计与实施*——盖斯定律

当前“盖斯定律”的教学中,注重加和法、虚拟路径法等解题模型的教学,缺乏在真实情境中对物质转化及其能量关系的理解,学生无法感受到盖斯定律在生产中的价值。本文以“能量视角下煤的气化对于提高煤的燃烧效率的意义”为研究主题,通过分析建模、实验验证、情境回归等认识并应用盖斯定律,从能量视角再认识煤的气化对于提高煤的燃烧效率的意义,并且认识到利用化学反应可以实现对能量进行调控,如对工业废热的再利用,深化能量守恒观和能源节约意识,达成提升学科核心素养的目标。     

On the isolated points of the surjective spectrum of a bounded operator

For a bounded operator acting on a complex Banach space, we show that if is not surjective, then is an isolated point of the surjective spectrum of if and only if , where is the quasinilpotent part of and is the analytic core for . Moreover, we study the operators for which . We show that for each of these operators , there exists a finite set consisting of Riesz points for such that and is connected, and derive some consequences.

     

VOx(x=1-5)团簇结构与稳定性的DFT研究

用密度泛函理论(DFT)的B3LYP方法在相对论有效实势（RECP）(O/6-311++g(d,p), V/lanl2dz)水平上对气态VOx(x=1-5)分子的几何构型, 振动频率, 电子亲和势和能级分布进行了理论研究. 通过对基态结构的几何参数分析发现, 它们的基态结构趋于立体结构. 其基态结构为: VO (4Σ), VO2 (2A1), VO3 (2A), VO4 (2A2), VO5 (4B2) . 对基态结构的垂直电离能, 电子性质和能级分布研究分析表明: 该系列分子最稳定的是VO4, 最不稳定的是VO. 该系列分子基态的平均VO键键长随氧原子数的增加而增长.     

First combined total reflection X-ray fluorescence and grazing incidence X-ray absorption spectroscopy characterization of aeolian dust archived in Antarctica and Alpine deep ice cores

Aeolian mineral dust archived in polar and mid latitude ice cores represents a precious proxy for assessing environmental and climatic variations at different timescales. In this respect, the identification of dust mineralogy plays a key role. In this work we performed the first preliminary X-ray absorption spectroscopy (XAS) experiments on mineral dust particles extracted from Antarctic and from Alpine firn cores using grazing incidence geometry at the Fe K-edge. A dedicated high vacuum experimental chamber was set up for normal-incidence and total-reflection X-Ray Fluorescence and Absorption Spectroscopy analyses on minor amounts of mineral materials at the Stanford Synchrotron Radiation Laboratory. Results show that this experimental technique and protocol allows recognizing iron inclusion mineral fraction on insoluble dust in the 1–10 µg range.     

近红外光谱法研究升温导致的尼龙1010结晶区域的变化

采用近红外光谱技术和二维相关分析法研究尼龙1010膜在升温过程中的结构变化. 为了排除非晶区域酰胺基团的影响, 事先对尼龙1010的样品膜进行了氘代, 并测量了其最终氘代率. 结果证明, 尼龙1010的结晶区域在升温过程中被逐渐破坏, 首先是其主链碳氢结构发生调整, 进一步影响到结合酰胺, 导致氢键作用减弱并最后生成自由胺基.     

A feasibility study on the use of Li(4)V(3)O(8) as a high capacity cathode material for lithium-ion batteries

Li(4)V(3)O(8) materials have been prepared by chemical lithiation by Li(2)S of spherical Li(1.1)V(3)O(8) precursor materials obtained by a spray-drying technique. The over-lithiated vanadates were characterised physically by using scanning electron microscopy (SEM) and X-ray diffraction (XRD), and electrochemically using galvanostatic charge-discharge and cyclic voltammetry measurements in both the half-cell (vs. Li metal) and full-cell (vs. graphite) systems. The Li(4)V(3)O(8) materials are stable in air for up to 5 h, with almost no capacity drop for the samples stored under air. However, prolonged exposure to air will severely change the composition of the Li(4)V(3)O(8) materials, resulting in both Li(1.1)V(3)O(8) and Li(2)CO(3). The electrochemical performance of these over-lithiated vanadates was found to be very sensitive to the conductive additive (carbon black) content in the cathode. When sufficient carbon black is added, the Li(4)V(3)O(8) cathode exhibits good cycling behaviour and excellent rate capabilities, matching those of the Li(1.1)V(3)O(8) precursor material, that is, retaining an average charge capacity of 205 mAh g(-1) at 2800 mA g(-1) (8C rate; 1C rate means full charge or discharge of a battery in one hour), when cycled in the potential range of 2.0-4.0 V versus Li metal. When applied in a non-optimised full cell system (vs. graphite), the Li(4)V(3)O(8) cathode showed promising cycling behaviour, retaining a charge capacity (Li(+) extraction) above 130 mAh g(-1) beyond 50 cycles, when cycled in the voltage range of 1.6-4.0 V, at a specific current of 117 mA g(-1) (C/3 rate).