基于神经网络的托卡马克能量约束时间预测

使用机器学习理论中的神经网络方法,根据通用逼近原理对能量约束时间的复杂函数进行逼近,采用托卡马克装置的典型实验数据,设计一种组合结构的神经网络。通过大量的调参试验,给出一套性能最好的参数组合,并与传统幂指数形式的多元线性回归方法进行准确性和数据集迁移能力的比较。结果表明：神经网络模型对于能量约束时间的预测准确率更高,回归性能更好,且具有一定的抗噪声能力,更适合作为能量约束时间的定标或预测工具。     

基于最新势能面的C(1D)+H2反应的环聚合分子动力学研究

本文利用环聚合分子动力学方法对C(¹D)+H₂反应开展了详细的理论研究. 计算中使用了最近构建的Zhang-Ma-Bian(ZMB)从头算势能面,该势能面对锥形交叉附近区域以及范德华区域均有精确的描述. 环聚合分子动力学计算得到的热反应速率常数与最新实验值吻合很好. 与前人计算结果比较,发现在?¹A′电子基态的ZMB-a势能面上获得的反应速率常数远大于前人构建的RKHS势能面上的结果,这是由于ZMB势能面上的范德华鞍具有与之前势能面上的范德华阱完全不同的动态学作用,表明环聚合分子动力学方法能够处理范德华作用引起的势能面拓扑结构所导致的动态学效应. 本文还揭示了b¹A′′电子激发态ZMB-b势能面以及量子效应对反应的重要性.     

基于全维高精度势能面对H+SO2→OH+SO反应的动力学研究

H+SO₂→OH+SO反应在燃烧、大气和星际化学中都扮演着重要角色. 它还是具有深势阱中间体形成的典型反应,是检验速率理论和提供有趣反应动力学现象的理想候选反应. 基于之前构建的全维高精度势能面,本文对该反应进行了准经典动力学研究. 在1400 K≤T≤2200 K的温度范围内,计算值重现了实验速率常数. 当反应物SO₂处于振-转基态,在31.0∽40.0 kcal/mol的碰撞能范围内,计算得到的积分反应截面随碰撞能增加;在40∽55 kcal/mol的碰撞能范围内,积分反应截面几乎不受碰撞能影响. 产物角度分布呈现对称的前后向双峰结构. 本文还分析了产物OH和SO的振动态分布.     

GW/BSE级别下的非绝热动力学模拟揭示桥连化学键对调控酞菁锌-富勒烯给体-受体复合物激发态弛豫过程的重要作用

本文采用基于多体格林函数方法和Bethe-Salpeter方程(GW/BSE)的电子结构计算方法和非绝热动力学模拟研究了两种不同桥连化学键构型(5-6构型和6-6构型)的酞菁锌-富勒烯(ZnPc-C₆₀)给受体复合物的激发态性质及其弛豫过程. 对于6-6构型,ZnPc-C₆₀的最低激发态S₁态为光谱明态,即ZnPc的局域激发(LE)态,因此,6-6构型的ZnPc-C₆₀在光激发之后几乎不会发生电荷分离过程. 相比之下,5-6构型的ZnPc-C₆₀的S₁态是C₆₀的LE态,为光谱暗态,而作为光谱明态的ZnPc的LE态的能量更高. 而且,在ZnPc和C₆₀的LE态之间还存在若干电荷转移(CT)态. 因此,电荷转移会在从高能的ZnPc的LE态到低能的C₆₀的LE态的弛豫过程中发生. GW/BSE级别的非绝热动力学模拟结果进一步验证了电子结构计算的结论,并给出了相关过程的时间尺度：从ZnPc到C₆₀的超快激发态能量转移过程在前200 fs完成;随后发生的是由C₆₀到ZnPc的超快空穴转移过程. 本工作表明不同的桥连化学键模式(即5-6和6-6构型)可用于调节ZnPc-C₆₀给体-受体复合物的激发态性质及其光电性质. 与此同时,本工作证明了GW/BSE级别的非绝热动力学方法是探索非周期性给体-受体复合物、有机金属配合物、量子点、纳米团簇等复杂体系的光诱导动力学的可靠工具.     

气体团簇离子束两步能量修形法的平坦化效应

本文提出采用气体团簇离子束的两步能量修形法来改善4H-SiC(1000)晶片表面形貌.先用15 keV的高能Ar团簇离子进行整体修形,再用5 keV的低能团簇离子优化表面.结果表明,在相同的团簇离子剂量下,与单一15 keV的高能团簇处理相比,两步法修形后的表面具有更低的均方根粗糙度,两者分别为1.05 nm和0.78 nm.本文还以原子级平坦表面为研究对象,揭示了载能团簇引起的半球形离子损伤(弧坑)与团簇能量的关系,及两步能量修形法在弧坑修复中的优势.在原子力显微镜表征的基础上,引入了二维功率谱密度函数,以直观全面地给出材料的表面形貌特征及其随波长(频率)的分布.结果表明,经任何能量的团簇离子轰击的表面,在0.05—0.20μm波长范围内,团簇轰击都能有效地降低粗糙度,而在0.02—0.05μm范围内,则出现了粗化效应,这是由于形成了半球形离子损伤,但第二步更低能量的团簇离子处理可以削弱这种粗化效应.     

Theoretical Study on the Hydrogen Bonding Interactions in Complexes of 5‐Hydroxytryptamine with Water

The energies, geometries and harmonic vibrational frequencies of 1:1 5‐hydroxytryptamine‐water (5‐HT‐H₂O) complexes are studied at the MP2/6‐311++G(d,p) level. Natural bond orbital (NBO), quantum theory of atoms in molecules (QTAIM) analyses and the localized molecular orbital energy decomposition analysis (LMO‐EDA) were performed to explore the nature of the hydrogen‐bonding interactions in these complexes. Various types of hydrogen bonds (H‐bonds) are formed in these 5‐HT‐H₂O complexes. The intermolecular C4H5^5‐HT···O^w H‐bond in HTW3 is strengthened due to the cooperativity, whereas no such cooperativity is found in the other 5‐HT‐H₂O complexes. H‐bond in which nitrogen atom of amino in 5‐HT acted as proton donors was stronger than other H‐bonds. Our researches show that the hydrogen bonding interaction plays a vital role on the relative stabilities of 5‐HT‐H₂O complexes.     

基于绿色氢科学理念构筑从低碳制氢到高效储氢的氢能体系

本文从低碳制氢和高效储氢的角度思考及探讨氢能体系绿色化发展过程中的关键科学问题.提出＂绿色氢科学＂理念与＂低碳制氢,高效储氢＂技术发展路线图,以期通过相关科学问题的认识,来构建具有高度原子经济性及可持续性的绿色氢能体系.     

Biofuels–Renewable Energy Sources: A Review

Biodiesel is biodegradable and nontoxic, and it significantly reduces toxic and other emissions when burned as a fuel. The advantages of biodiesel as diesel fuel are its portability, ready availability, renewability, higher combustion efficiency, non-toxicity, higher flash point, and lower sulfur and aromatic content, higher cetane number, and higher biodegradability. The major disadvantages of biodiesel are its higher viscosity, lower energy content, higher cloud point and pour point, higher nitrogen oxide (NO_x) emissions, lower engine speed and power, injector coking, engine compatibility, high price, and greater engine wear. The technical disadvantages of biodiesel/fossil diesel blends include problems with fuel freezing in cold weather, reduced energy density, and degradation of fuel under storage for prolonged periods. The sources of biodiesel are vegetable oils and fats. The direct use of vegetable oils and/or oil blends is generally considered to be unsatisfactory and impractical for both direct injection and indirect type diesel engines because of their high viscosities and low volatilities injector coking and trumpet formation on the injectors, higher level of carbon deposits, oil ring sticking, and thickening and gelling of the engine lubricant oil, acid composition. Biodiesel is obtained by transesterifying triglycerides with methanol. A popular variation of the batch transesterification process which needs high alcohol/acid ratio (several separation problems and high corrosivity and toxicity) is the use of continuous stirred tank reactors in series. This continuous process is heterogeneous and is based on reactive distillation. The key factor is the selection of the right and effective solid catalyst which leads to reduction of energy consumption and investments at all.     

Encapsulating Sulfur into Hierarchically Ordered Porous Carbon as a High‐Performance Cathode for Lithium–Sulfur Batteries

A three‐dimensional (3D) hierarchical carbon–sulfur nanocomposite that is useful as a high‐performance cathode for rechargeable lithium–sulfur batteries is reported. The 3D hierarchically ordered porous carbon (HOPC) with mesoporous walls and interconnected macropores was prepared by in situ self‐assembly of colloidal polymer and silica spheres with sucrose as the carbon source. The obtained porous carbon possesses a large specific surface area and pore volume with narrow mesopore size distribution, and acts as a host and conducting framework to contain highly dispersed elemental sulfur. Electrochemical tests reveal that the HOPC/S nanocomposite with well‐defined nanostructure delivers a high initial specific capacity up to 1193 mAh g^?1 and a stable capacity of 884 mAh g^?1 after 50 cycles at 0.1 C. In addition, the HOPC/S nanocomposite exhibits high reversible capacity at high rates. The excellent electrochemical performance is attributed exclusively to the beneficial integration of the mesopores for the electrochemical reaction and macropores for ion transport. The mesoporous walls of the HOPC act as solvent‐restricted reactors for the redox reaction of sulfur and aid in suppressing the diffusion of polysulfide species into the electrolyte. The “open” ordered interconnected macropores and windows facilitate transportation of electrolyte and solvated lithium ions during the charge/discharge process. These results show that nanostructured carbon with hierarchical pore distribution could be a promising scaffold for encapsulating sulfur to approach high specific capacity and energy density with long cycling performance.     

Photosynthetic Antenna‐Reaction Center Mimicry with a Covalently Linked Monostyryl Boron‐Dipyrromethene–Aza‐Boron‐Dipyrromethene–C60 Triad

An efficient functional mimic of the photosynthetic antenna‐reaction center has been designed and synthesized. The model contains a near‐infrared‐absorbing aza‐boron‐dipyrromethene (ADP) that is connected to a monostyryl boron‐dipyrromethene (BDP) by a click reaction and to a fullerene (C₆₀) using the Prato reaction. The intramolecular photoinduced energy and electron‐transfer processes of this triad as well as the corresponding dyads BDP‐ADP and ADP‐C₆₀ have been studied with steady‐state and time‐resolved absorption and fluorescence spectroscopic methods in benzonitrile. Upon excitation, the BDP moiety of the triad is significantly quenched due to energy transfer to the ADP core, which subsequently transfers an electron to the fullerene unit. Cyclic and differential pulse voltammetric studies have revealed the redox states of the components, which allow estimation of the energies of the charge‐separated states. Such calculations show that electron transfer from the singlet excited ADP (¹ADP*) to C₆₀ yielding ADP^.+‐C₆₀^.? is energetically favorable. By using femtosecond laser flash photolysis, concrete evidence has been obtained for the occurrence of energy transfer from ¹BDP* to ADP in the dyad BDP‐ADP and electron transfer from ¹ADP* to C₆₀ in the dyad ADP‐C₆₀. Sequential energy and electron transfer have also been clearly observed in the triad BDP‐ADP‐C₆₀. By monitoring the rise of ADP emission, it has been found that the rate of energy transfer is fast (≈10¹¹ s^?1). The dynamics of electron transfer through ¹ADP* has also been studied by monitoring the formation of C₆₀ radical anion at 1000 nm. A fast charge‐separation process from ¹ADP* to C₆₀ has been detected, which gives the relatively long‐lived BDP‐ADP^.+C₆₀^.? with a lifetime of 1.47 ns. As shown by nanosecond transient absorption measurements, the charge‐separated state decays slowly to populate mainly the triplet state of ADP before returning to the ground state. These findings show that the dyads BDP‐ADP and ADP‐C₆₀, and the triad BDP‐ADP‐C₆₀ are interesting artificial analogues that can mimic the antenna and reaction center of the natural photosynthetic systems.