Boosted sodium ion storage performance in MnO_(2):Understanding the bond angle-mediated orbital overlap in MnO_(6)units for fast charge transfer

Symmetric six oxygen-coordinated Mn structural units(MnO6)in MnO2 with small Mn–O orbital overlap hamper electron transfer rates during energy storage.Herein,we report a novel bond angle modulation strategy to manipulate Mn–O orbital overlap in MnO2 through the construction of Mn vacancies(MnO2-VMn),aiming at expediting electron transfer,and thus enhancing energy storage performance.Both experimental and theoretical results disclose that the amplification of Mn–O–Mn bond angles exclusively augments the Mn(dx2-y2)-O(py)orbital overlap and triggers the electron redistribution in MnO2-VMn,inducing an augmented Mn dx2-y2 electron occupation.This heightened presence of active electrons in the Mn dx2-y2 orbital paves the way for accelerating electron transfer and ion transfer in MnO2-VMn.Notably,MnO2-VMn delivers an improved specific capacitance of 425 F g−1 at 1 A g−1 and a superior rate capacity of 265 F g−1 at 20 A g−1.Furthermore,an asymmetric supercapacitor(MnO2-VMn//AC ASC)was fabricated,exhibiting a high energy density of 64.3 Wh kg−1 at a power density of 1000 W kg−1.Furthermore,theoretical insights uncover the profound implications of metal–oxygen–metal bond angle regulation on interatomic orbital overlap modulation.These revelations illuminate pathways for the design of advanced energy storage materials.

Near-optimal cumulative longitude low-thrust orbit transfer

The indirect method for the continuous low-thrust near minimum cumulative longitude orbit transfer problem is addressed.The movement of the satellite is described by the Gauss equation using the modified equinoctial elements and replacing time as the system independent variable by the cumulative longitude.The maximum principle is adapted to design the optimal control in order to minimize the final cumulative longitude, and the twopoint-boundary-value problem is derived from the orbit transfer problem.The single shooting method is applied in a numerical experiment, and the simulations demonstrate that the orbit transfer mission is fulfilled and the product of the maximal thrust and the minimum cumulative longitude is near constant.

Design of low-energy transfer from lunar orbit to asteroid in the Sun-Earth-Moon system

Asteroid exploration trajectories which start from a lunar orbit are investigated in this work.It is assumed that the probe departs from lunar orbit and returns to the vicinity of Earth,then escapes from the Earth by performing a perigee maneuver.A low-energy transfer in Sun-EarthMoon system is adopted.First,the feasible region of lowenergy transfer from lunar orbit to perigee within 5 000 km height above the Earth surface in Sun-Earth-Moon system is calculated and analyzed.Three transfer types are found,i.e.,large maneuver and fast transfers,small maneuver and fast transfers,and disordered and slow transfers.Most of feasibility trajectories belong to the first two types.Then,the lowenergy trajectory leg from lunar orbit to perigee and a heliocentric trajectory leg from perigee to asteroid are patched by a perigee maneuver.The optimal full-transfer trajectory is obtained by exploiting the differential evolution algorithm.Finally,taking 4179 Toutatis asteroid as the target,some low-energy transfer trajectories are obtained and analyzed.

Optimal aeroassisted symmetric transfer between coplanar elliptical orbits

The problem of optimal aeroassisted symmetric transfer between elliptical orbits is concerned.The complete trajectory is assumed as consisting of two impulsive velocity changes at the beginning and the end of an interior atmospheric subarc,where the vehicle is controlled via the lift coefficient and thrust.The corresponding dynamic equations are built and bounded controls are considered.For the purpose of optimization computation,the equations are normalized.In order to minimize the total fuel consumption,the geocentric radius of initial elliptical transfer orbital perigee and controls during atmospheric flight should all be optimized.It is an optimal control problem which involves additional parameter optimization.To solve the problem,a two-level optimization method denoted by ＂genetic algorithm ＋ Gauss pseudospectral method＂ is adopted：the genetic algorithm is used for parameter optimization and the Gauss pseudospectral method is used for optimal control problems.The flow chart of simulation is given.On this basis,the issue of more realistic modeling with two finite-thrust subarcs in the nonatmospheric part of the trajectory is simultaneously addressed.The orbital transfer problem is transformed to three continuous optimal control problems,and the constraints at different times are given,which are respectively solved by using the Gauss pseudospectral method.The obtained numerical results indicate that the optimal thrust control is of bangbang type.The minimum-fuel trajectory in the atmosphere consists of aeroglide,aerocruise and aeroglide.They are compared with the results of pure impulsive model,and the conclusions that a significant fuel saving will be achieved by synergetic maneuver are drawn.

Calibration chain design based on integrating sphere transfer radiometer for SI-traceable on-orbit spectral radiometric calibration and its uncertainty analysis

In order to satisfy the requirement of SI-traceable on-orbit absolute radiation calibration transfer with high accuracy for satellite remote sensors,a transfer chain consisting of a fiber coupling monochromator（FBM） and an integrating sphere transfer radiometer（ISTR） was designed in this paper.Depending on the Sun,this chain based on detectors provides precise spectral radiometric calibration and measurement to spectrometers in the reflective solar band（RSB） covering 300–2500 nm with a spectral bandwidth of 0.5–6 nm.It shortens the traditional chain based on lamp source and reduces the calibration uncertainty from 5% to 0.5% by using the cryogenic radiometer in space as a radiometric benchmark and trap detectors as secondary standard.This paper also gives a detailed uncertainty budget with reasonable distribution of each impact factor,including the weak spectral signal measurement with uncertainty of 0.28%.According to the peculiar design and comprehensive uncertainty analysis,it illustrates that the spectral radiance measurement uncertainty of the ISTR system can reach to 0.48%.The result satisfies the requirements of SI-traceable on-orbit calibration and has wider significance for expanding the application of the remote sensing data with high-quality.

Exploring the effect of aggregation-induced emission on the excited state intramolecular proton transfer for a bis-imine derivative by quantum mechanics and our own n-layered integrated molecular orbital and molecular mechanics calculations

We theoretically investigate the excited state intramolecular proton transfer(ESIPT) behavior of the novel fluorophore bis-imine derivative molecule HNP which was designed based on the intersection of 1-(hydrazonomethyl)-naphthalene-2-ol and 1-pyrenecarboxaldehyde. Especially, the density functional theory(DFT) and time-dependent density functional theory(TDDFT) methods for HNP monomer are introduced. Moreover, the "our own n-layered integrated molecular orbital and molecular mechanics"(ONIOM) method(TDDFT:universal force field(UFF)) is used to reveal the aggregation-induced emission(AIE) effect on the ESIPT process for HNP in crystal. Our results confirm that the ESIPT process happens upon the photoexcitation for the HNP monomer and HNP in crystal, which is distinctly monitored by the optimized geometric structures and the potential energy curves. In addition, the results of potential energy curves reveal that the ESIPT process in HNP will be promoted by the AIE effect. Furthermore, the highest occupied molecular orbital(HOMO) and lowest unoccupied molecular orbital(LUMO) for the HNP monomer and HNP in crystal have been calculated. The calculation demonstrates that the electron density decrease of proton donor caused by excitation promotes the ESIPT process. In addition, we find that the variation of atomic dipole moment corrected Hirshfeld population(ADCH) charge for proton acceptor induced by the AIE effect facilitates the ESIPT process. The results will be expected to deepen the understanding of ESIPT dynamics for luminophore under the AIE effect and provide insight into future design of high-efficient AIE compounds.

The Solution of Optimal Two-Impulse Transfer between Elliptical Orbits with Plane Change

The optimizing total velocity increment Δv needed for orbital maneuver between two elliptic orbits with plane change is investigated. Two-impulse orbital transfer is used based on a changing of transfer velocities concept due to the changing in the energy. The transferring has been made between two elliptic orbits having a common centre of attraction with changing in their planes in standard Hohmann transfer with the terminal orbit which is elliptic orbit and not circular. We develop a treatment based on the elements of elliptic orbits a1,e1, a2,e2, and?aT,eT of the initial orbit, final orbit and transferred orbit respectively. The first impulse Δv1 at the perigee induces a rotation of the orbital plane by ?which will be minimized. The second impulse Δv2 at apogee is induced an angle ?to product the final elliptic orbit. The total plane change required . We calculate the total impulse Δv and minimize by optimizing angle of plane’s variation . We obtain a polynomial equation of six degrees on the two transfer angles between neither two elliptic orbits ?and . The solution obtained numerically, using programming code of MATHEMATICA V10, with no condition on the eccentricity or the semi-major axis of the initial, transformed, and the final orbits. We find that there are constrains on the transfer angles and α. For αit must be between 40°and 160°, and there is no solution if αis less than 40°and bigger than 160°and ?takes the values less than 40°. The minimum total velocity increments obtained at the value of ?less than 25°and& alpha;equal to 160°. This is an interesting result in orbital transfer problem in which the change of orbital plane is necessary for the transferring.

Frontier Orbitals, Combustion and Redox Transfer from a Fermionic-Bosonic Orbital Perspective

Oxygenations are highly exergonic, yet combustion of organic matter is not spontaneous in an atmosphere that is 21% O2. Electrons are fermions with a quantum spin number s of 1/2ħ. An orbital containing a single electron with s = 1/2 is fermionic. Orbitals can contain a maximum of two electrons with antiparallel spins, i.e., spin magnetic quantum numbers ms of 1/2 and -1/2. An orbital filled by an electron couple has s = 0 and bosonic character. The multiplicity of a reactant is defined as |2(S)| + 1 where S is the total spin quantum number. The Wigner spin conservation rules state that multiplicity is conserved. The transmission coefficient κ of absolute reaction rate theory also indicates the necessity for spin conservation. Burning is fermionic combustion that occurs when sufficient energy is applied to a bosonic molecule to cause homolytic bond cleavage yielding fermionic products capable of reaction with the bifermionic frontier orbitals of triplet multiplicity O2. Neutrophil leucocytes kill microorganisms by bosonic combustion and employ two mechanisms for changing the multiplicity of O2 from triplet to singlet. Microorganisms, composed of bosonic singlet multiplicity molecules, do not directly react with bifermionic O2, but are highly susceptible to electrophilic attack by bosonic electronically excited singlet molecular oxygen (1O2*). Hydride ion (H-) transfer is the common mode of cytoplasmic redox metabolism. Bosonic transfer of an orbital electron couple protects from damage by obviating fermionic reaction with bifermionic O2. Bosonic coupled electron transfer raises the consideration that quantum tunneling might be involved in facilitating such redox transfer.

VLBI观测对转发式测距GEO卫星定轨精度的贡献分析

联合甚长基线干涉测量(very long baseline interferometry,VLBI)时延数据与转发式(orbit determination by transfer tracking,ODTT)测距数据能够有效提高地球静止轨道(geostationary earth orbit,GEO)卫星定轨精度。参照位置精度衰减因子(position dilution of precision,PDOP)的改变,研究不同VLBI基线时延数据与转发式测距数据的联合对GEO卫星定轨精度的改善,可为特定条件下联合观测时VLBI基线的最优选择提供参考。基于中国科学院国家授时中心宽带VLBI系统和转发式测轨系统的实测数据,开展中星12号GEO卫星的定轨试验。试验结果表明定轨精度的提高与PDOP的降低成正相关。相比于转发式单独定轨,联合VLBI系统中的喀什—三亚基线,PDOP降低了3.00,定轨精度提高了11.48%;联合VLBI系统中的吉林—喀什基线,PDOP降低了3.38,定轨精度提高了14.73%;联合VLBI系统中的吉林—三亚基线,PDOP降低了6.90,定轨精度提高了19.75%;联合VLBI系统中的吉林—三亚和吉林—喀什两条基线,PDOP降低了9.94,定轨精度提高了27.23%。

一种超参数自适应航天器交会变轨策略优化方法

利用强化学习技术,本文提出了一种超参数自适应的燃料最优地球同步轨道(GEO)航天器交会变轨策略优化方法。首先,建立了GEO航天器交会Lambert变轨模型。以变轨时刻为决策变量、燃料消耗为适应度函数,使用改进式综合学习粒子群算法(ICLPSO)作为变轨策略优化的基础方法。其次,考虑到求解的最优性和快速性,重新设计了以粒子群算法(PSO)优化结果为参考基线的奖励函数。使用一族典型GEO航天器交会工况训练深度确定性策略梯度神经网络(DDPG)。将DDPG与ICLPSO组合为强化学习粒子群算法(RLPSO),从而实现算法超参数根据实时迭代收敛情况的自适应动态调整。最后,仿真结果表明与PSO、综合学习粒子群算法(CLPSO)相比,RLPSO在较少迭代后即可给出适应度较高的规划结果,减轻了迭代过程中的计算资源消耗。

Perturbed low-thrust geostationary orbit transfer guidance via polynomial costate estimation

This paper proposes an optimal,robust,and efficient guidance scheme for the perturbed minimum-time low-thrust transfer toward the geostationary orbit.The Earth’s oblateness perturbation and shadow are taken into account.It is difficult for a Lyapunov-based or trajectory-tracking guidance method to possess multiple characteristics at the same time,including high guidance optimality,robustness,and onboard computational efficiency.In this work,a concise relationship between the minimum-time transfer problem with orbital averaging and its optimal solution is identified,which reveals that the five averaged initial costates that dominate the optimal thrust direction can be approximately determined by only four initial modified equinoctial orbit elements after a coordinate transformation.Based on this relationship,the optimal averaged trajectories constituting the training dataset are randomly generated around a nominal averaged trajectory.Five polynomial regression models are trained on the training dataset and are regarded as the costate estimators.In the transfer,the spacecraft can obtain the real-time approximate optimal thrust direction by combining the costate estimations provided by the estimators with the current state at any time.Moreover,all these computations onboard are analytical.The simulation results show that the proposed guidance scheme possesses extremely high guidance optimality,robustness,and onboard computational efficiency.

通过氟掺杂调控TiO_(2)的d带中心以增强光催化产H_(2)O_(2)活性

光催化产双氧水(H_(2)O_(2))以太阳光、水和空气中的氧气作为原料,将光能转变为化学能,是一种绿色高效节能环保的新技术,具有较好的应用前景.光催化产H_(2)O_(2)主要包括三个关键步骤:(1)催化剂在高能入射光激发下产生光生电子和空穴;(2)光生电子-空穴对分离并迁移到催化剂表面;(3)光生电子与催化剂表面吸附的氧气发生反应生成超氧自由基,其继续与水和光生电子反应,产生H_(2)O_(2).因此,氧气在催化剂表面吸附性能的强弱对光催化产H_(2)O_(2)的性能有着重要影响.d带中心理论表明,金属的d带能级高低决定了催化剂表面活性位点对小分子物质的吸附强度,能级越高,催化剂对小分子物质的吸附能力越强.TiO_(2)具有制备简单、无毒、理化性质稳定、导价带位置跨越多个氧化还原电位等诸多优势,在光催化生产H_(2)O_(2)领域具有较好的应用前景.提升TiO_(2)的d带中心可以提高其对小分子物质如O_(2)的吸附性能,有效提升其光催化产H_(2)O_(2)的活性.本文从氟离子掺杂提升TiO_(2)的d带中心增强对O_(2)的吸附性能入手,通过第一性理论计算、电子顺磁共振实验、飞秒瞬态吸收光谱等方法研究光生载流子的传输机理,阐明F/TiO_(2)光催化产H_(2)O_(2)活性增强机制,并对TiO_(2)光催化产H_(2)O_(2)的前景提出了展望.首先,分别以钛酸四异丙酯和氟化铵作为钛源和氟源,通过溶胶-凝胶法结合高温煅烧制得了F/TiO_(2)光催化剂.第一性理论计算结果表明,F-体相掺杂导致TiO_(2)的电荷分布不均匀,使得d带中心上移,从而增强TiO_(2)与表面吸附O_(2)的相互作用,降低表面氧的吸附能,最终提高光催化生成H_(2)O_(2)的效率.电子顺磁共振实验结果表明,晶格中F-离子的存在诱导了还原性Ti^(3+)中心的形成,这些还原性Ti^(3+)中心可以提供电荷补偿所需的额外电子.O_(2)温度程序解吸实验结果表明,F/TiO_(2)对O_(2)的化学吸附能力高于纯TiO_(2),说明较低的反键轨道占用率可以增强Ti^(3+)对O_(2)的吸附.飞秒瞬态吸收光谱结果表明,光生电子从F/TiO_(2)的导带转移到Ti^(3+)表面态和表面F-离子上,加速了光生电子和空穴的分离;光生电子与吸附在F/TiO_(2)表面的O_(2)发生反应,加速了H_(2)O_(2)的生成.光催化产H_(2)O_(2)性能实验结果表明,F-掺杂TiO_(2)后,光催化生成H_(2)O_(2)的产率由277μmol·g^(-1)·h^(-1)提高到了467μmol·g-1·h^(-1).循环实验结果表明,F/TiO_(2)使用前后形貌和晶体结构几乎没有改变,且循环实验后氧空位和Ti3+中心依然存在,说明制得的F/TiO_(2)光催化剂具有良好的稳定性.综上所述,本文借助第一性理论计算并结合实验结果,从d带中心调控的角度揭示了F/TiO_(2)光催化产H_(2)O_(2)活性提高的机理,阐明了光催化产H_(2)O_(2)的反应机制.本研究为优化光催化剂与氧气之间的吸附强度,提高光催化产H_(2)O_(2)的性能提供了一种新策略,可为后续光催化产H_(2)O_(2)技术的改进和应用提供参考.

共线平动点中心流形上的轨道转移问题

圆形限制性三体问题共线平动点附近的平动点轨道由于其独特的动力学特性,在深空探测任务中有着重要价值,这些轨道间的轨道转移问题值得进行系统性研究.针对平动点轨道的计算与延拓,提出了一种基于数值的系统性计算平动点轨道的方法以及状态伴随法的轨道稳定维持策略.在此基础上,通过对大量平动点轨道不变流形以及平动点相空间中心流形的研究,设计了一套通过脉冲机动实现平动点轨道间轨道转移的系统性解决方案.该方法充分利用平动点动力学特性,在仿真验证中证实了方案的有效性,为平动点轨道转移研究提供了新的思路.

Impulsive orbit control for spacecraft around asteroid

An impulse feedback control law to change the mean orbit elements of spacecraft around asteroid is presented. First, the mean orbit elements are transferred to the osculating orbit elements at the burning time. Then, the feedback control law based on Gauss’s perturbation equations of motion is given. And the impulse control for targeting from the higher circulation orbit to the specified periapsis is developed. Finally, the numerical simulation is performed and the simulation results show that the presented impulse control law is effective.

Effect of Spacecraft Aerodynamics and Heat Shield Characteristics on Optimal Aeroassisted Transfer

A spacecraft designed to operate in a planetary atmosphere must have an adequate heat shield to withstand the high heat fluxes and heat loads that are generated by aerodynamic heating. Very often, the mass of the thermal protection system is a significant fraction of the total mass of the vehicle. In contrast, performing maneuvers in the atmosphere, that would be very costly in terms of propellant consumption if they were performed completely outside of the atmosphere in a classic way, is a very attractive prospective technique. The advantages and disadvantages in terms of total mass spared must be determined. The mission investigated involves an aeroassisted coplanar transfer from a high to a low Earth orbit. The approach uses a combination of three propulsive impulses in space together with an aerodynamic maneuver in the atmosphere. The heat shield adopted is fully ablative, given the expected high values of the entering heat flux. The convenience of the aeroassisted maneuver and the influence of the parameters involved are evaluated in comparison to a conventional Hohmann transfer. In particular, a parametric analysis is performed by varying the following characteristics of the vehicle: aerodynamic efficiency, mass-to-surface ratio, deorbit impulse, and initial altitude of the orbit. The influence of the thermal protection system is examined by assessing the impact of the type of ablative material employed, the thermal safety factor, and the allowable temperature for the adhesive layer on the substructure. The analysis is conducted with a highly representative thermal model by coupling the dynamic and thermal analyses and using a genetic optimizer. The optimization methodology and the thermal model are completely original. The results indicate the importance of choosing low-density ablative materials, of adopting a suitable thermal safety factor, and of choosing high-performance adhesives. The optimal trajectories obtained correspond to a zero second propulsive impulse.

星历模型下地月自由返回全飞行过程轨道设计

面向载人登月任务需要,针对星历模型下具备自由返回能力的地月转移轨道设计问题进行了研究。在三体模型下对地月三维自由返回轨道进行了求解,得到了地月空间内的自由返回轨道分布情况。在二体模型假设下对近月段的三脉冲变轨进行了求解,给出了变平面机动的计算方法。进一步提出了两轮逐次优化修正策略,分别以高度和再入走廊为主要约束,采用内点法和SQP算法在高精度星历模型下对自由返回轨道初值进行逐次优化修正。之后,采用SQP算法在星历模型下对近月三脉冲变轨进行优化修正,得到了星历模型下的自由返回+近月三脉冲变轨地月转移策略。仿真校验结果表明本文提出的方法能够在给定约束下有效求解星历模型下具备自由返回能力的地月转移轨道,为载人登月任务的转移轨道设计提供参考。

基于迁移深度强化学习的低轨卫星跳波束资源分配方案

针对低轨(LEO)卫星场景下,传统资源分配方案容易造成特定小区资源分配无法满足需求的问题,该文提出一种基于迁移深度强化学习(TDRL)的低轨卫星跳波束资源分配方案。首先,该方案联合星上缓冲信息、业务到达情况和信道状态,以最小化卫星上数据包平均时延为目标,建立支持跳波束技术的低轨卫星资源分配优化模型。其次,针对低轨卫星网络的动态多变性,该文考虑动态随机变化的通信资源和通信需求,采用深度Q网络(DQN)算法利用神经网络作为非线性近似函数。进一步,为实现并加速深度强化学习(DRL)算法在其他目标任务中的收敛过程,该文引入迁移学习(TL)概念,利用源卫星学习的调度任务快速寻找目标卫星的波束调度和功率分配策略。仿真结果表明,该文所提出的算法能够优化卫星服务过程中的时隙分配,减少数据包的平均传输时延,并有效提高系统的吞吐量和资源利用效率。

自旋轨道矩协助自旋转移矩驱动磁化强度翻转

以磁隧道结/重金属层组成的三端口磁隧道结为理论模型,通过对包含自旋转移矩和自旋轨道矩的Landau-Lifshitz-Gilbert(LLG)方程做线性化稳定性分析,研究了自旋轨道矩协助自旋转移矩驱动的磁化强度翻转.发现在自旋轨道矩协助下,磁矩的翻转时间极大减小,翻转时间随自旋轨道矩电流密度的增大而减小,且自旋转移矩和自旋轨道矩的结合可实现零磁场的磁化翻转.另外,相比自旋轨道矩的类阻尼项,类场项在磁化强度的翻转中起着主导作用,且自旋轨道矩类场项的出现也可以减小磁化强度的翻转时间,磁化强度翻转时间随自旋轨道矩类场项强度的增大而减小.

The influence of the Dresselhaus spin-orbit coupling on the tunnelling magnetoresistance in ferromagnet/ insulator /semiconductor/ insulator /ferromagnet tunnel junctions

This paper investigates the effect of Dresselhaus spin orbit coupling on the spin-transport properties of ferromagnet/insulator/semiconductor/insulator/ferromagnet double-barrier structures. The influence of the thickness of the insulator between the ferromagnet and the semiconductor on the polarization is also considered. The obtained results indicate that （i） the polarization can be enhanced by reducing the insulator layers at zero temperature, and （ii） the tunnelling magnetoresistance inversion can be illustrated by the influence of the Dresselhaus spin-orbit coupling effect in the double-barrier structure. Due to the Dresselhaus spin-orbit coupling effect, the tunnelling magnetoresistance inversion occurs when the energy of a localized state in the barrier matches the Fermi energy EF of the ferromagnetic electrodes.

Calculations of state-selective differential cross sections for charge transfer in collisions between O^(3+) and H_2

The non-dissociative charge-transfer processes in collisions between O^3＋ and H2 are investigated by using the quantum-mechanical molecular-orbital coupled-channel （QMOCC） method. The adiabatic potentials and radial coupling matrix elements utilized in the QMOCC calculations are obtained with the spin-coupled valence-bond approach. Electronic and vibrational state-selective differential cross sections are presented for projectile energies of 0.1, 1.0 and 10.0eV/u in the H2 orientation angles of 45° and 89°. The electronic and the vibrational state-selective differential cross sections show similar behaviours： they decrease as the scattering angle increases, and beyond a specific angle the oscillating structures appear. Moreover, it is also found that the vibrational state-selective differential cross sections are strongly orientation-dependent, which provides a possibility to determine the orientations of molecule H2 by identifying the vibrational state-selective differential scattering processes.