Orbital magnetization in semiconductors

National Natural Science Foundation of China 60821061 60776061 10604010 60776063

Orbital Magnetization of Quantum Spin Hall Insulator Nanoparticles

Both spin and orbital degrees of freedom contribute to the magnetic moment of isolated atoms. However, when inserted in crystals, atomic orbital moments are quenched because of the lack of rotational symmetry that protects them when isolated. Thus, the dominant contribution to the magnetization of magnetic materials comes from electronic spin. Here we show that nanoislands of quantum spin Hall insulators can host robust orbital edge magnetism whenever their highest occupied Kramers doublet is singly occupied, upgrading the spin edge current into a charge current. The resulting orbital magnetization scales linearly with size, outweighing the spin contribution for islands of a few nm in size. This linear scaling is specific of the Dirac edge states and very different from Schrodinger electrons in quantum rings. By modeling Bi(111) flakes, whose edge states have been recently observed, we show that orbital magnetization is robust with respect to disorder, thermal agitation, shape of the island, and crystallographic direction of the edges, reflecting its topological protection.

Structural, electronic, and magnetic entropy contributions of the orbital order-disorder transition in LaMnO(3)

Measurements of X-ray diffraction, electrical resistivity, and magnetization are reported across the Jahn-Teller phase transition in LaMnO(3). Using a thermodynamic equation, we obtained the pressure derivative of the critical temperature (T(JT)), dT(JT)/dP = -28.3 K GPa(-1). This approach also reveals that 5.7(3)J(mol K)(-1) comes from the volume change and 0.8(2)J(mol K)(-1) from the magnetic exchange interaction change across the phase transition. Around T(JT), a robust increase in the electrical conductivity takes place and the electronic entropy change, which is assumed to be negligible for the majority of electronic systems, was found to be 1.8(3)J(mol K)(-1).

Natural remanent magnetization (NRM) from ODP Site 1263 covering magnetochron C20r and C21n and high-resolution bulk carbon isotope (d13C) records from Sites 702 and 1263

To explore cause and consequences of past climate change, very accurate age models such as those provided by the astronomical timescale (ATS) are needed. Beyond 40 million years the accuracy of the ATS critically depends on the correctness of orbital models and radioisotopic dating techniques. Discrepancies in the age dating of sedimentary successions and the lack of suitable records spanning the middle Eocene have prevented development of a continuous astronomically calibrated geological timescale for the entire Cenozoic Era. We now solve this problem by constructing an independent astrochronological stratigraphy based on Earth's stable 405 kyr eccentricity cycle between 41 and 48 million years ago (Ma) with new data from deep-sea sedimentary sequences in the South Atlantic Ocean. This new link completes the Paleogene astronomical timescale and confirms the intercalibration of radioisotopic and astronomical dating methods back through the Paleocene-Eocene Thermal Maximum (PETM, 55.930 Ma) and the Cretaceous-Paleogene boundary (66.022 Ma). Coupling of the Paleogene 405 kyr cyclostratigraphic frameworks across the middle Eocene further paves the way for extending the ATS into the Mesozoic.

Time-Dependent Density Functional Molecular Orbital and Excited State Calculations on Bis(porphyrinyl)butadiynes in the Monocationic, Neutral, Monoanionic, and Dianionic Oxidation States

We report a theoretical study of the multiple oxidation states (1+, 0, 1−, and 2−) of a meso,meso-linked diporphyrin, namely bis[10,15,20-triphenylporphyrinatozinc(II)-5-yl]butadiyne (4), using Time-Dependent Density Functional Theory (TDDFT). The origin of electronic transitions of singlet excited states is discussed in comparison to experimental spectra for the corresponding oxidation states of the close analogue bis{10,15,20-tris[3‘,5‘-di-tert-butylphenyl]porphyrinatozinc(II)-5-yl}butadiyne (3). The latter were measured in previous work under in situ spectroelectrochemical conditions. Excitation energies and orbital compositions of the excited states were obtained for these large delocalized aromatic radicals, which are unique examples of organic mixed-valence systems. The radical cations and anions of butadiyne-bridged diporphyrins such as 3 display characteristic electronic absorption bands in the near-IR region, which have been successfully predicted with use of these computational methods. The radicals are clearly of the “fully delocalized” or Class III type. The key spectral features of the neutral and dianionic states were also reproduced, although due to the large size of these molecules, quantitative agreement of energies with observations is not as good in the blue end of the visible region. The TDDFT calculations are largely in accord with a previous empirical model for the spectra, which was based simplistically on one-electron transitions among the eight key frontier orbitals of the C4 (1,4-butadiyne) linked diporphyrins.

Super-orbital re-entry in Australia : laboratory measurement, simulation and flight observation

There are large uncertainties in the aerothermodynamic modelling of super-orbital re-entry which impact the design of spacecraft thermal protection systems (TPS). Aspects of the thermal environment of super-orbital re-entry flows can be simulated in the laboratory using arc- and plasma jet facilities and these devices are regularly used for TPS certification work [5]. Another laboratory device which is capable of simulating certain critical features of both the aero and thermal environment of super-orbital re-entry is the expansion tube, and three such facilities have been operating at the University of Queensland in recent years[10]. Despite some success, wind tunnel tests do not achieve full simulation, however, a virtually complete physical simulation of particular re-entry conditions can be obtained from dedicated flight testing, and the Apollo era FIRE II flight experiment [2] is the premier example which still forms an important benchmark for modern simulations. Dedicated super-orbital flight testing is generally considered too expensive today, and there is a reluctance to incorporate substantial instrumentation for aerothermal diagnostics into existing missions since it may compromise primary mission objectives. An alternative approach to on-board flight measurements, with demonstrated success particularly in the ‘Stardust’ sample return mission, is remote observation of spectral emissions from the capsule and shock layer [8]. JAXA’s ‘Hayabusa’ sample return capsule provides a recent super-orbital reentry example through which we illustrate contributions in three areas: (1) physical simulation of super-orbital re-entry conditions in the laboratory; (2) computational simulation of such flows; and (3) remote acquisition of optical emissions from a super-orbital re entry event.

Image-based visual servoing for the super-orbital re-entry of Hayabusa spacecraft

This paper presents an image-based visual servoing system that was used to track the atmospheric Earth re-entry of Hayabusa. The primary aim of this ground based tracking platform was to record the emission spectrum radiating from the superheated gas of the shock layer and the surface of the heat shield during re-entry. To the author's knowledge, this is the first time that a visual servoing system has successfully tracked a super-orbital re-entry of a spacecraft and recorded its pectral signature. Furthermore, we improved the system by including a simplified dynamic model for feed-forward control and demonstrate improved tracking performance on the International Space Station (ISS). We present comparisons between simulation and experimental results on different target trajectories including tracking results from Hayabusa and ISS. The required performance for tracking both spacecraft is demanding when combined with a narrow field of view (FOV). We also briefly discuss the preliminary results obtained from the spectroscopy of the Hayabusa's heat shield during re-entry.

Switching radical stability by pH-induced orbital conversion

In most radicals the singly occupied molecular orbital (SOMO) is the highest-energy occupied molecular orbital (HOMO); however, in a small number of reported compounds this is not the case. In the present work we expand significantly the scope of this phenomenon, known as SOMO-HOMO energy-level conversion, by showing that it occurs in virtually any distonic radical anion that contains a sufficiently stabilized radical (aminoxyl, peroxyl, aminyl) non-pi-conjugated with a negative charge (carboxylate, phosphate, sulfate). Moreover, regular orbital order is restored on protonation of the anionic fragment, and hence the orbital configuration can be switched by pH. Most importantly, our theoretical and experimental results reveal a dramatically higher radical stability and proton acidity of such distonic radical anions. Changing radical stability by 3-4 orders of magnitude using pH-induced orbital conversion opens a variety of attractive industrial applications, including pH-switchable nitroxide-mediated polymerization, and it might be exploited in nature.

Tuning of magnetization in vertical graphenes by plasma-enabled chemical conversion of organic precursors with different oxygen content

Different magnetization in vertical graphenes fabricated by plasma-enabled chemical conversion of organic precursors with various oxygen atom contents and bonding energies was achieved. The graphenes grown from fat-like precursors exhibit magnetization up to 8 emu g−1, whereas the use of sugar-containing precursors results in much lower numbers. A relatively high Curie temperature exceeding 600 K was also demonstrated.

Single layer lead iodide: Computational exploration of structural, electronic and optical properties, strain induced band modulation and the role of spin-orbital-coupling

Graphitic like layered materials exhibit intriguing electronic structures and thus the search for new types of two-dimensional (2D) monolayer materials is of great interest for developing novel nano-devices. By using density functional theory (DFT) method, here we for the first time investigate the structure, stability, electronic and optical properties of monolayer lead iodide (PbI2). The stability of PbI2 monolayer is first confirmed by phonon dispersion calculation. Compared to the calculation using generalized gradient approximation, screened hybrid functional and spin–orbit coupling effects can not only predicts an accurate bandgap (2.63 eV), but also the correct position of valence and conduction band edges. The biaxial strain can tune its bandgap size in a wide range from 1 eV to 3 eV, which can be understood by the strain induced uniformly change of electric field between Pb and I atomic layer. The calculated imaginary part of the dielectric function of 2D graphene/PbI2 van der Waals type hetero-structure shows significant red shift of absorption edge compared to that of a pure monolayer PbI2. Our findings highlight a new interesting 2D material with potential applications in nanoelectronics and optoelectronics.

The impact of orbital errors on the estimation of satellite clock errors and PPP

Precise satellite orbit and clocks are essential for providing high accuracy real-time PPP (Precise Point Positioning) service. However, by treating the predicted orbits as fixed, the orbital errors may be partially assimilated by the estimated satellite clock and hence impact the positioning solutions. This paper presents the impact analysis of errors in radial and tangential orbital components on the estimation of satellite clocks and PPP through theoretical study and experimental evaluation. The relationship between the compensation of the orbital errors by the satellite clocks and the satellite-station geometry is discussed in details. Based on the satellite clocks estimated with regional station networks of different sizes (∼100, ∼300, ∼500 and ∼700 km in radius), results indicated that the orbital errors compensated by the satellite clock estimates reduce as the size of the network increases. An interesting regional PPP mode based on the broadcast ephemeris and the corresponding estimated satellite clocks is proposed and evaluated through the numerical study. The impact of orbital errors in the broadcast ephemeris has shown to be negligible for PPP users in a regional network of a radius of ∼300 km, with positioning RMS of about 1.4, 1.4 and 3.7 cm for east, north and up component in the post-mission kinematic mode, comparable with 1.3, 1.3 and 3.6 cm using the precise orbits and the corresponding estimated clocks. Compared with the DGPS and RTK positioning, only the estimated satellite clocks are needed to be disseminated to PPP users for this approach. It can significantly alleviate the communication burdens and therefore can be beneficial to the real time applications.

Structure of the benzene center dot center dot center dot ICI complex: A UVPES and ab initio molecular orbital study

UVPES studies and ab initio and DFT computations have been done on the benzene...ICl complex; electron spectral data and computed orbital energies show that donor orbitals are stabilized and acceptor orbitals are destabilized due to complexation. Calculations predict an oblique structure for the complex in which the interacting site is a C=C bond center in the donor and iodine atom in the acceptor, in full agreement with earlier experimental reports. BSSE-corrected binding energies closely match the enthalpy of complexation reported, and the NBO analysis clearly reveals the involvement of the pi orbital of benzene and the sigma* orbital of ICl in the complex.

Nucleophilic additions to 4-substituted snoutanones: getting a measure of long range electrostatic and orbital control of pi-face selectivity

Pentacyclic ketones 10a-e (snoutan-9-ones) undergo nucleophilic additions with the same facial preference as the corresponding norsnoutanones 9a-e, but with markedly reduced selectivity, revealing the involvement of electrostatic effects in the former and implying the importance of hyperconjugative orbital interactions in determining pi-face selectivity in the latter systems.

Magnetization, magnetotransport and electron magnetic resonance studies of nanoparticles and nanowires of Pr0.5Sr0.5MnO3

In this paper, we present the preparation and characterization of nanoparticles and nanowires of Pr0.5Sr0.5MnO3 (PSMO). The main results of this investigation are as follows: (a) a comparison with the properties of the bulk material shows that the ferromagnetic (FM) transition at 270 K remains unaffected but the anti-ferromagnetic (AFM) transition at TN = 150 K disappears in the nanoparticles, (b) the size induced ground state magnetic phase (below 150 K) is predominantly FM, coexisting with a residual AFM phase, and (c) the temperature dependence of magnetic anisotropy shows complex behaviour, being higher in the nanoparticles at high temperatures and lower at moderately lower temperatures in comparison with the bulk. The results obtained from the extensive magnetization, magnetotransport and electron magnetic resonance studies made on various samples are presented and discussed in detail.