Ring Current Research Articles

Topological characterizations on hexagonal and rectangular tessellations of antikekulenes and its computed spectral, nuclear magnetic resonance and electron spin resonance characterizations

AbstractTessellations of antikekulenes are of interest from the standpoints of antiaromaticity, ring currents, unusual ‐electron characteristics, magnetism and their highly reactive nature. Although precursors of antikekulenes have been synthesized, up to now synthesis of antikekulenes has been proven to be formidably difficult. Yet they are predicted to have intriguing properties and their antiaromatic nature together with a combination of four and six‐membered rings makes them intriguing candidates for theoretical indices. In the present study, we have computed the topological indices of antikekulene by employing graph‐theoretical cut methods that simplify the parent tessellations of antikekulenes into simpler graphs. We have derived exact mathematical expressions of several topological descriptors for hexagonal and rectangular antikekulene structures. Furthermore we have obtained the graph‐spectral properties, algebraic structure counts, resonance stabilization and delocalization energies as well as nuclear magnetic resonance and electron spin resonance spectroscopic patterns of the two tessellations of antikekulenes.

Magnetic field-enhanced oxygen reduction reaction for electrochemical hydrogen peroxide production with different cerium oxide nanostructures

We investigated cerium oxide nanoparticles of various morphologies (nanosheets, nanocubes, and nanoparticles) supported on carbon Vulcan XC-72 for the two-electron oxygen reduction reaction (ORR). A continuous magnetic field (2000 Oe) was used for the first time in the literature. The best results were for 5 % (w/w) CeO2 for all three different morphologies, more than doubling the ring current, enhancing the hydrogen peroxide selectivity from 51 % (Vulcan XC-72) to 84–89 %, and modifying the onset potential to lesser negative values. The presence of the magnetic field led to even higher ring currents with 5 % (w/w) CeO2, H2O2 selectivity from 54 % (Vulcan XC-72) to 88–96 % and changing even more the onset potential. Those results were correlated with the Zeeman effect, the Lorentz force, generating magnetohydrodynamic effects, the Kelvin force, and the formation of Bound Magnetic Polarons. This pioneering research introduces an innovative approach, highlighting the potential of an external continuous magnetic field.

New Perspectives on Delocalization Pathways in Aromatic Molecular Chameleons.

This study comprehensively analyzes the magnetically induced current density of polycyclic compounds labeled as "aromatic chameleons" since they can arrange their π-electrons to exhibit aromaticity in both the ground and the lowest triplet state. These compounds comprise benzenoid moieties fused to a central skeleton with 4n π-electrons and traditional magnetic descriptors are biased due to the superposition of local magnetic responses. In the S0state, our analysis reveals that the molecular constituent fragments preserve their (anti)aromatic features in agreement with two types of resonant structures: one associated with aromatic benzenoids and the other with a central antiaromatic ring. Regarding the T1state, a global and diatropic ring current is revealed. Our aromaticity study is complemented with advanced electronic and geometric descriptors to consider different aspects of aromaticity, particularly important in the evaluation of excited state aromaticity. Remarkably, these descriptors consistently align with the general features on the main delocalization pathways in polycyclic hydrocarbons with fused rings of 4n π-electron rings. Moreover, our work demonstrates an inverse correlation between the singlet-triplet energy difference and the antiaromatic character of the central ring in S0.

Ring current electron precipitation during the 17 March 2013 geomagnetic storm: Underlying mechanisms and their effect on the atmosphere

Electron and ion fluxes at energies of ∼10 keV−1 MeV can change by orders of magnitude during geomagnetically active periods. This can lead to intensification of particle precipitation into the Earth's atmosphere. The process further affects atmospheric chemistry, which may impact weather and climate on the Earth’s surface. In this study, we concentrate on ring current electrons, and investigate precipitation mechanisms using a numerical model based on the Fokker-Planck equation. We focus on a study of the main precipitation mechanisms, and their connection with atmospheric parameters. We investigate the 17 March 2013 storm using the convection–diffusion 4-Dimensional Versatile Electron Radiation Belt (VERB-4D) code, that allows us to quantify the impact of the storm on the electron ring current, and the resulting electron precipitation. We validate our results against observations from the Polar Operational Environmental Satellites (POES) mission, the low Earth orbiting meteorological satellites National Oceanic and Atmospheric Administration (NOAA-15,-16,-17,-18,-19), and Meteorological Operational Satellite MetOp-02, as well as the Van Allen Probes, and produce a data set of precipitating fluxes that covers an energy range from 10 keV to 1 MeV. We calculate the altitude-dependent atmospheric ionization rates, a prerequisite for atmospheric models to estimate effects of geomagnetically active periods on chemical and physical variability of the atmosphere at high latitudes. Atmospheric ionization rates are validated against Atmospheric Ionization during Substorm (AIMOS 2.1-Aisstorm) and Special Sensor Ultraviolet Spectrographic Imagers (SSUSI) values, and show good agreement at high geomagnetic latitudes during the storm time.

The anti-aromatic dianion and aromatic tetraanion of [18]annulene.

π-Conjugated macrocycles behave differently from analogous linear chains because their electronic wavefunctions resemble a quantum particle on a ring, leading to aromaticity or anti-aromaticity. [18]Annulene, (CH)18, is the archetypal non-benzenoid aromatic hydrocarbon. Molecules with circuits of 4n + 2 π electrons, such as [18]annulene (n = 4), are aromatic, with enhanced stability and diatropic ring currents (magnetic shielding inside the ring), whereas those with 4n π electrons, such as the dianion of [18]annulene, are expected to be anti-aromatic and exhibit the opposite behaviour. Here we use 1H NMR spectroscopy to re-evaluate the structure of the [18]annulene dianion. We also show that it can be reduced further to an aromatic tetraanion, which has the same shape as the dianion. The crystal structure of the tetraanion lithium salt confirms its geometry and reveals a metallocene-like sandwich, with five Li+ cations intercalated between two [18]annulene tetraanions. We also report a heteroleptic sandwich, with [18]annulene and corannulene tetraanion decks.

Substitution Effect of a Single Nitrogen Atom on π-Electronic Systems of Linear Polycyclic Aromatic Hydrocarbons (PAHs): Theoretically Visualized Coexistence of Mono- and Polycyclic π-Electron Delocalization.

We theoretically investigated the nitrogen substitution effect on the molecular structure and π-electron delocalization in linear nitrogen-substituted polycyclic aromatic hydrocarbons (N-PAHs). Based on the optimized molecular structures and magnetic field-induced parameters of fused bi- and tricyclic linear N-PAHs, we found that the local π-electron delocalization of subcycles (e.g., mono- and bicyclic constituent moieties) in linear N-PAHs is preserved, despite deviation from ideal structures of parent monocycles. The introduction of a fused five-membered ring with a pyrrolic N atom (N-5MR) in linear N-PAHs significantly perturbs the π-electronic condition of the neighboring fused six-membered ring (6MR). Monocyclic pyrrole exhibits substantial bond length alternations, strongly influencing the π-electronic systems of both the fused N-5MR and 6MR in linear N-PAHs, depending on the location of shared covalent bonds. A fused six-membered ring with a graphitic N atom in an indolizine moiety cannot generate monocyclic π-electron delocalization but instead contributes to the formation of polycyclic π-electron delocalization. This is evidenced by bifurcated diatropic ring currents induced by an external magnetic field. In conclusion, the satisfaction of Hückel's 4n + 2 rule for both mono- and polycycles is crucial for understanding the overall π-electron delocalization. It is crucial to consider the unique characteristics of the three types of substituted N atoms and the spatial arrangement of 5MR and 6MR in N-PAHs.

Magnetic Trapping of Galactic Cosmic Rays in the Outer Heliosheath and Their Preferential Entry into the Heliosphere

This paper examines the geometry of interstellar magnetic field lines close to the boundary of the heliosphere in the direction of the unperturbed local interstellar magnetic field, where the field lines are spread apart by the heliopause (HP). Such field parting establishes a region of weaker magnetic field of about 300 au in size in the northern hemisphere that acts as a giant magnetic trap affecting the propagation of galactic cosmic rays (GCRs). The choice of an analytic model of the magnetic field in the very local interstellar medium allows us to qualitatively study the resulting magnetic field draping pattern while avoiding unphysical dissipation across the HP-impeding numerical magnetohydrodynamic (MHD) models. We investigate GCR transport in the region exterior to the heliosphere, including the magnetic trap, subject to guiding center drifts, pitch angle scattering, and perpendicular diffusion. The transport coefficients were derived from Voyager 1 observations of magnetic turbulence in the VLISM. Our results predict a ring current of energetic ions drifting around the interior of the magnetic trap. It is also demonstrated that GCRs cross the HP for the first time preferentially through a crescent-shaped region between the magnetic trap and the upwind direction. The paper includes results of MHD modeling of the heliosphere that provide the coordinates of the center of the magnetic trap in ecliptic coordinates. In addition to the heliosphere, we examine several extreme field draping configurations that could describe the astrospheres of other stars.

Understanding Aromaticity in [5]Helicene-Bridged Cyclophanes: A Comprehensive Study.

This study explores the aromaticity of doubly [5]helicene-bridged (1,4)cyclophane and triply [5]helicene-bridged (1,3,5)cyclophane via calculations of the magnetic response and of electronic aromaticity indices. The primary objective is to assess the π-electron delocalization to determine whether they sustain global ring currents associated with π aromaticity. The molecules show local ring currents in the presence of an external magnetic field. The ring currents flow diatropically in the stacked six-membered rings and in the helicene arms. However, these π currents are not interconnected due to the discontinuity of the π delocalization at the C-C single bonds connecting the central six-membered rings to the helicene arms. Electronic indices suggest that the helicene-arm systems have significantly smaller electron delocalization than benzene. The reduction in the delocalization does not compromise their ability to exhibit ring currents in the presence of an external magnetic field. The analysis provides further evidence that the magnetic criteria yield a different degree of aromaticity for the helicene arms than obtained in the calculation of the electronic aromaticity indices. However, both approaches confirm that the studied molecules are not globally aromatic.

Quantum control of flying doughnut terahertz pulses.

The ability to manipulate the multiple properties of light diversifies light-matter interaction and light-driven applications. Here, using quantum control, we introduce an approach that enables the amplitude, sign, and even configuration of the generated light fields to be manipulated in an all-optical manner. Following this approach, we demonstrate the generation of "flying doughnut" terahertz (THz) pulses. We show that the single-cycle THz pulse radiated from the dynamic ring current has an electric field structure that is azimuthally polarized and that the space- and time-resolved magnetic field has a strong, isolated longitudinal component. We apply the flying doughnut pulse for a spectroscopic measurement of the water vapor in ambient air. Pulses such as these will serve as unique probes for spectroscopy, imaging, telecommunications, and magnetic materials.

Tetraquinolines; four linked quinoline units or porphyrinoids.

Tetraquinolines (TEQs) have been recently synthesized and proposed to be a new member of the porphyrinoid family with highly distorted, nonplanar, geometries. In this contribution by studying several molecules, closely related to TEQs, we have suggested that the origin of the nonplanarity of TEQs and their counterparts is a combination of steric strain and the propensity of the molecules to avoid antiaromaticity. The tendency of TEQs to coordinate with doubly charged metal ions can be interpreted in terms of their transition from potential antiaromaticity to nonaromaticity. Even metal-coordinated TEQs do not sustain diatropic ring currents. Although full planarization is not possible because of steric strain, doubly oxidized TEQs and their counterparts sustain moderate global diatropic ring currents and partially planarize. The nature of current density in the molecules is studied in the light of Steiner-Fowler selection rules.

Pyrrole and Pyridine Peripherally Fused Perylene: Columnar Packing, Anti-Kasha Dual Emission and Reactive Oxygen Species Generation

Simultaneously fusing pyrrole and pyridine at perylene’s opposite edges is facilely realized in this work, yielding PerNN and its various derivatives. All targets demonstrate global diamagnetic ring current. Benefiting from...

Group 13 five- and six-membered rings with rare 2π aromaticity.

According to Hückel's rule, cyclic species are aromatic if they have 4n + 2 (n = 0, 1, 2, etc.) π electrons. However, large aromatic rings (atom number > 4) with minimum 2π electrons (i.e., n = 0) are rather rare because of the structural instability stemming from the deficient π electrons compared to the ring size. To date, the largest 2π-aromatic ring is a five-membered Ga5 core reported in a recent experiment. Herein, density functional theory calculations predicted seven inverse-sandwich Na2(MH)5 and half-sandwich Ca(MH)5 or Ca(MH)6 (M = Al, Ga or In) structures. They all have planar central five- or six-membered Al/Ga/In rings, rather negative binding energies and large HOMO-LUMO gaps. Their dianionic metal rings exhibit obvious aromatic characters and appreciable diatropic ring currents due to the good delocalization of 2π electrons donated by the Na/Ca metals. Interestingly, they also have novel collective bonding with the Na/Ca atoms interacting with both the metal ring and surrounding H atoms. These metalloaromatic rings not only greatly enrich the precious family of 2π aromatics, but also increase the maximum ring atom number from five to six, thus paving the way for Hückel-type 2π-aromatic large rings.

中国区域Dst指数数据集（2010–2022）

The axisymmetric disturbance of the Geomagnetic field caused by the ring current can be quantified using the Disturbance storm-time (Dst) index. Due to the asymmetry of the ring current during the storm time, there are s notable variations in the geomagnetic disturbance levels at different locations, which cannot be accurately reflected by the globally averaged Dst index. In this paper, we collected and calculated the geomagnetic data of the Chinese Meridian Project in Lasa, Chengdu, Wuhan and Hangzhou, so as to produce a dataset of Dst Indexes in China. This dataset includes Chinese Dst indexes from 2010 to 2022, with a total of 109,608 entries of data. In addition to the comprehensive collection of Dst indexes, this dataset can be used to better describe the geomagnetic disturbances in the Chinese region and is expected to furnish valuable data for regional space weather research in China.

Synthesis of C3-substituted chlorophyll-a derivatives fused by a π-conjugated E-ring and their physical properties with unique near-infrared absorption

Chlorophylls (Chls) are one of the most important pigments for the light-harvesting systems in photosynthesis. Methyl pheophorbide-a derivative fused by a π-conjugated E-ring with the C131=C132 double bond was found as a synthetic example of the unique Chl-a derivatives, which showed split Soret absorption bands in the purple and ultraviolet-A regions and a broad absorption band at a near-infrared (NIR) region as its monomeric state, but not its self-aggregated species. The 3-vinyl group of the Chl-a derivative was chemically transformed into ethyl, formyl, hydroxymethyl, and dialkoxymethyl groups. All the resulting chlorins exhibited unique wide bands at a NIR region. The substitution effect on the peaks of their wide NIR bands was similar to that on the sharp redmost Qy maxima at a visible region of the corresponding pheophorbides with the C131–C132 single bond. Protons at the C5-, C10-, and C20-positions as well as of the peripheral C2-, C3-, C7-, and C8-substituents of methyl 3-substituted 131,132-didehydro-131-deoxo-pheophorbides-a were upfield-shifted in 1H nuclear magnetic resonance, compared with those of intact pheophorbides. The shifts were ascribed to the less ring current of the cyclic tetrapyrroles by π-conjugation of the E-ring. The non-fluorescent C3-substituted Chl-a derivatives could be useful as new materials absorbing NIR wavelength light.

Theoretical investigation on the optical response of the artificial magnetic–plasmonic nanoclusters

Bottom-up nanofabrication, organizing colloidal nanoparticles into ordered clusters with structural and functional complexity, provides an alternative to yield nanometric smart structures unachievable in traditional top-down approaches. Those remarkable structures assembled of colloidal nanoparticles possessing optical properties feature exotic optical responses under the illumination of incident light, showing highly dependent on the particle separation, composition, and arrangement. Here, the nanoscale electromagnetic coupling in magnetic–plasmonic nanoparticle clusters is analyzed by using a 3D full-wave computational model, and the mechanism of the resonances in a split-ring resonator out of magnetic–plasmonic nanoparticle building blocks is also illustrated. In particular, once assembling those artificial molecules (split-ring resonator) into secondary metamaterial superstructures, such as split-ring resonator dimer and Y-shaped structures, a series of exotic optical responses are presented due to the greatly enhanced near-field coupling of nanoparticles and the generation of antiparallel ring currents in the asymmetrical superstructure, exhibiting flexible sensitivity to the changes of the surrounding environment. Besides, the H-shaped arrangement exhibits high sensitivity with Q = 50.5 at λ = 2.02 μm. Our finding provides a platform for yielding complex structures with flexible tunability of the optical response through arranging those assembled artificial molecules into complex secondary structures, allowing for the development of smart sensing devices.

Aromaticity Reversal Induced by Vibrations in Cyclo[16]carbon.

Aromaticity is typically regarded as an intrinsic property of a molecule, correlated with electron delocalization, stability, and other properties. Small variations in the molecular geometry usually result in small changes in aromaticity, in line with Hammond's postulate. For example, introducing bond-length alternation in benzene and square cyclobutadiene by modulating the geometry along the Kekulé vibration gradually decreases the magnitude of their ring currents, making them less aromatic and less antiaromatic, respectively. A sign change in the ring current, corresponding to a reversal of aromaticity, typically requires a gross perturbation such as electronic excitation, addition or removal of two electrons, or a dramatic change in the molecular geometry. Here, we use multireference calculations to show how movement along the Kekulé vibration, which controls bond-length alternation, induces a sudden reversal in the ring current of cyclo[16]carbon, C16. This reversal occurs when the two orthogonal π systems of C16 sustain opposing currents. These results are rationalized by a Hückel model which includes bond-length alternation, and which is combined with a minimal model accounting for orbital contributions to the ring current. Finally, we successfully describe the electronic structure of C16 with a "divide-and-conquer" approach suitable for execution on a quantum computer.

RAM‐SCB Runs on Request at CCMC

AbstractThe Ring current–Atmosphere interactions Model (RAM) with Self‐Consistent magnetic (B) field (SCB) combines a large‐scale kinetic model of ring current plasma with a three‐dimensional (3‐D) force‐balanced model of the terrestrial magnetic field. RAM‐SCB simulates the evolution of major ion species (H+, O+, and He+ by default) and electrons as a function of azimuth, radial distance, energy, and pitch angle. Simulation outputs include the Dst index, and pressure and differential flux of the modeled species, thus providing benefit as a science code and to inform surface charging hazard within the model domain. Version 2.2 of this open‐source simulation code has now—as of 8 August 2023—been made available for Runs‐On‐Request via the Community Coordinated Modeling Center.

A Model of Hourly Variations of the Near‐Earth Magnetic Field Generated in the Inner Magnetosphere and Its Induced Counterpart

AbstractWe present a new model of the near‐Earth magnetospheric field produced by electric currents in the inner magnetosphere and the associated induced magnetic field. The model is designed to track hourly variations of these fields and accounts for their local time asymmetries. It is built by applying spherical harmonic analysis to vector measurements from the ground observatory network at low and mid‐latitudes. The primary and induced fields are separated with an approach in the time domain that uses a a priori radially‐symmetric electric conductivity model of the Earth. The model coefficients are computed at one‐hour time steps between 1997 and 2022. This model is shown to be consistent to within a few nT with previously developed indices which track the magnetospheric ring current. It is also validated against data from the Swarm, CHAMP and Øersted satellites. The fit to satellite data is comparable to that of the CHAOS‐7.15 model for geomagnetically quiet times, and improved by up to 20% on some components for geomagnetically moderate and active times. We attribute these differences mostly to a better representation of local time asymmetries, both on average and during individual geomagnetic storms. This model can be used in various applications, such as investigating the properties of the magnetospheric field and its sources and separating the magnetospheric field from the fields of other sources in geomagnetic field modeling.

Study of particle dynamics in presence of ring current driven magnetic field variations

The development of the ring current through a westward circulation of energetic ions around the Earth in the low latitude region during geomagnetic storms has been known to us for the past several decades. The symmetric part of the ring current exists in the form of a ring around the Earth at a distance of ≈3–7Re from the center of the Earth. The location and strength of the ring current is mainly controlled by the interplanetary solar wind conditions. The presence of such external current forms the additional mini magnetic dipole in the vicinity of the Earth’s space, which eventually affects the geomagnetic field configuration. The magnetic field produced due to the ring current opposes the geomagnetic field inside and adds to the geomagnetic field outside the location of the ring current. This scenario has been modelled in this paper by using a circular loop of uniform current around the Earth to represent the ring current flow around the Earth. The aim of the present study is to understand the overall changes in the magnetic field and its influence on the radiation belt energetic (MeV range) electrons and protons during a geomagnetic storm. The model calculations suggest the formation of low and high magnetic field regions (here referred to as dent and hump) in the Earth’s magnetosphere due to intense westward ring current. The size and position of these low and high magnetic field regions are controlled by the strength and location of the ring current. It is found that both the altitudinal reach and mirror point of the bouncing-drifting radiation belt energetic particles are significantly affected by the presence of the dent and the hump in the magnetic field driven by the ring current. The decrease in ground magnetic field of 1700 nT or more, which is similar to the geomagnetic field variation observed during the historic Carrington event, is possible with the peak ring current strength of 20–30 MA situated at a distance of 2Re or less from the center of the Earth.

Ultrafast switching of persistent electron and hole ring currents in a molecule

Ultrafast switching of persistent electron and hole ring currents in a molecule