A mapping of the electron localization function for the silica polymorphs: evidence for domains of electron pairs and sites of potential electrophilic attack

The electron localization function, η, evaluated for first-principles geometry optimized model structures generated for quartz and coesite, reveals that the oxide anions are coordinated by two hemispherically shaped η-isosurfaces located along each of the SiO bond vectors comprising the SiOSi angles. With one exception, they are also coordinated by larger banana-shaped isosurfaces oriented perpendicular to the plane centered in the vicinity of the apex of each angle. The hemispherical isosurfaces, ascribed to domains of localized bond-pair electrons, are centered ～0.70 Å along the bond vectors from the oxide anions and the banana-shaped isosurfaces, ascribed to domains of localized nonbonding lone-pair electrons, are centered ～0.60 Å from the apex of the angle. The oxide anion comprising the straight SiOSi angle in coesite is the one exception in that the banana-shaped isosurface is missing; however, it is coordinated by two hemispherically shaped isosurfaces that lie along the bond vectors. In the case of a first-principles model structure generated for stishovite, the oxide anion is coordinated by five hemispherically shaped η-isosurfaces, one located along each of the three SiO bond vectors (ascribed to domains of bonding-electron pairs) that are linked to the anion with the remaining two (ascribed to domains of nonbonding-electron pairs) located on opposite sides of the plane defined by three vectors, each isosurface at a distance of ～0.5 Å from the anion. The distribution of the five isosurfaces is in a one-to-one correspondence with the distribution of the maxima displayed by experimental Δρ and theoretical ??²ρ maps. Isosurface η maps calculated for quartz and the (HO) ₃ SiOSi(OH) ₃ molecule also exhibit maxima that correspond with the (3,?3) maxima displayed by distributions of ??²ρ. Deformation maps observed for the SiOSi bridges for the silica polymorphs and a number of silicates are similar to that calculated for the molecule but, for the majority, the maxima ascribed to lone-pair features are absent. The domains of localized nonbonding-electron pair coordinating the oxide anions of quartz and coesite provide a basis for explaining the flexibility and the wide range of the SiOSi angles exhibited by the silica polymorphs with four-coordinate Si. They also provide a basis for explaining why the SiO bond length in coesite decreases with increasing angle. As found in studies of the interactions of solute molecules with a solvent, a mapping of η-isosurfaces for geometry-optimized silicates is expected to become a powerful tool for deducing potential sites of electrophilic attack and reactivity for Earth materials. The positions of the features ascribed to the lone pairs in coesite correspond with the positions of the H atoms recently reported for an H-doped coesite crystal.     

Planetary,solar and astrophysical relativistic electrons: Common energization mechanisms?

Direct observations or deduced analysis indicate clearly that formation of intense fluxes of relativistic electrons is an important ingredient in the evolution of numerous active magnetized plasma systems. Examples of relativistic electron energization include the recovery phase of a planetary magnetic storm, post solar flare coronal activity and the afterglow of gamma ray bursts. It is suggested that there exists a universal mechanism, which may explain electron energization at the vastly different magnetized plasma environments. The favorite configuration consists of an inhomogeneous magnetic field anchored at a given magnetic structure and excitation of whistler waves due to external injection of low-energy non-isotropic electrons. The energization proceeds as a bootstrap process due to interaction with the propagating whistler waves along the inhomogeneous magnetic field.     

Distribution of free electrons in the galactic plane

A method is proposed for constructing a map of the electron density distribution in the galactic plane. Data on the dispersion measures DM of more than 1500 pulsars and their distances, found by an independent method, are used. The independent distances of the pulsars are estimated using an empirical relation of the form L=γP ^α Ṗ ^β W ^δ between the radio luminosity L of the pulsars and their periods P, the rate of change Ṗ. of their periods, and the half width W of their pulses. A map of the electron density distribution in the galactic plane within a ±400 pc layer is provided. __________ Translated from Astrofizika, Vol. 49, No. 2, pp. 277–287 (May 2006).     

Sources of SEP Acceleration during a Flare – CME Event

A high-speed, halo-type coronal mass ejection (CME), associated with a GOES M4.6 soft X-ray flare in NOAA AR 0180 at S12W29 and an EIT wave and dimming, occurred on 9 November 2002. A complex radio event was observed during the same period. It included narrow-band fluctuations and frequency-drifting features in the metric wavelength range, type III burst groups at metric – hectometric wavelengths, and an interplanetary type II radio burst, which was visible in the dynamic radio spectrum below 14 MHz. To study the association of the recorded solar energetic particle (SEP) populations with the propagating CME and flaring, we perform a multi-wavelength analysis using radio spectral and imaging observations combined with white-light, EUV, hard X-ray, and magnetogram data. Velocity dispersion analysis of the particle distributions (SOHO and Wind in situ observations) provides estimates for the release times of electrons and protons. Our analysis indicates that proton acceleration was delayed compared to the electrons. The dynamics of the interplanetary type II burst identify the burst source as a bow shock created by the fast CME. The type III burst groups, with start times close to the estimated electron-release times, trace electron beams travelling along open field lines into the interplanetary space. The type III bursts seem to encounter a steep density gradient as they overtake the type II shock front, resulting in an abrupt change in the frequency drift rate of the type III burst emission. Our study presents evidence in support of a scenario in which electrons are accelerated low in the corona behind the CME shock front, while protons are accelerated later, possibly at the CME bow shock high in the corona.     

Constraining Galactic pγ Interactions with Cosmic Ray Electron and Positron Spectra

High energy protons produced by various sources of cosmic rays, e.g., supernova remnants, pulsar wind nebulae, active galactic nuclei and gamma-ray bursts, participate in Pγ and pp interactions. Although pp interactions may be the dominant mechanism in our Galaxy, it is unclear how important pγ process is. We show that the upper bound on the fraction of total number of protons participating in pγ interactions inside all Galactic astrophysical sources of cosmic rays is 10%.     

>0.3 MeV高能电子注入辐射带槽区事件的分析与预报

本文利用低高度太阳同步轨道系列卫星NOAA/POES从1996年到2006年的>0.3 MeV高能电子观测数据,分析了>0.3 MeV高能电子注入辐射带槽区的特征,研究了注入槽区事件与行星际条件、太阳活动和地磁扰动之间的联系.研究表明>0.3 MeV高能电子注入辐射带槽区事件与磁暴的发生密切相关,注入事件的发生与太阳活动的强度有一定的相关性.在此研究的基础上,本文通过分析辐射带槽区>0.3 MeV高能电子通量和Dst指数的相关性,提出了利用Dst指数推算辐射带槽区>0.3 MeV高能电子通量的方法,继而给出了可行的辐射带槽区高能电子辐射环境的预警模式.     

高能电子爆发与绕月卫星表面电位大幅下降的联动效应

"嫦娥"一号、二号绕月飞行经历地球磁尾边界层区域时,分别在2007年11月26日—2008年2月5日和2010年10月3日—2011年2月28日,发现了15次月球轨道0.1~2 MeV电子急剧增加(Bursts of 0.1~2 MeV Energetic Electrons,BEE),卫星周围等离子体离子加速的现象.统计研究表明,这类现象发生在稳定太阳风和弱行星际磁场条件下,且无显著空间环境扰动事件发生时,离子的加速滞后于高能电子爆发,离子能量的变化与高能电子通量的时间演化正相关,地球磁鞘内侧或边界层过渡区域是该类现象的高发区,离子能量增加时卫星表面电位大幅下降可达负几千伏.为了研究高能电子爆发与绕月卫星表面电位变化的关系及其对月球表面电位的影响,本文用电流平衡法建立绕月卫星和月球表面充电模型,并假设能量电子(2eV~2 MeV)满足幂律谱的分布,模拟急剧增加的能量电子对卫星和月球表面电位的影响.模拟结果表明,能量电子急剧增加使得绕月卫星和月球表面电位大幅下降;能量电子总流量1011 cm-2时,绕月卫星和月球表面充电电位可达负上千伏;月球充电到大的负电位的时间仅为卫星充电时间的1/10.鉴于高能电子急剧增加事件的高发生率(~125次/年),能量电子急剧增加使得绕月卫星表面电位大幅下降的发生率应大于实测等离子体离子加速现象的发生率(~25次/年).     

Low-temperature crystal structures of stibnite implying orbital overlap of Sb 5s2 inert pair electrons

The crystal structure of stibnite [Sb₂S₃, Pnma, a=11.314(2), b=3.837(2), c=11.234(3) Å, V= 487.7(3) ų at 293 K] was refined in situ at 230, 173, and 128 K. It is a major characteristic of the structure that the Sb–S secondary bonds enclosing Sb 5s² inert lone-pair electrons at 293 K are significantly shorter than the corresponding sum of the Sb and S van der Waals radii. Concerning the temperature dependence, although both the polyhedral volume and the cation eccentricity of the two SbS₇ polyhedra exhibit continuous contractions with decreasing temperature, the sphericity values remain constant, indicating isotropic shrinkage. Consequently, the geometries of Sb 5s² inert lone-pair electrons and ligand atoms remain unchanged at low temperatures. This is because the crystal structure of stibnite at low temperature induces contraction with attractive interactions, which is called the orbital overlap between Sb 5s² inert lone-pair electrons and ligand orbitals to maintain the coordination environment. In this case, Sb 5s² lone-pair electrons are not inert, but active. Such orbital overlaps of inert lone-electron pairs can provide a reasonable explanation for shorter secondary bonds and lower band gap energy of the binary compounds containing heavy elements such as Sb, Te, Pb, and Bi, which are key factors in tracing the origins of color, luster, and semiconductivity of their minerals or compounds.