激励电压对沿面介质阻挡放电特性的影响分析

近年来,沿面介质阻挡放电(SDBD)用作大气压下气流控制的等离子体激励器因其众多的优点受到了广泛的关注.然而,国内外对沿面介质阻挡放电及其应用的研究尚处于探索阶段,对其放电特性的影响因素缺乏规律性的认识.因此,对SDBD相关特性和影响因素进行研究具有重要理论意义和应用价值.本文使用频率5～20 kHz,峰值电压0～30 kV的可调正弦交流电源激励大气压环境下的SDBD装置.通过调节激励电压大小,研究了其与SDBD放电特性之间的关系,对等离子体放电电流、放电形貌、功率损耗、诱导气流以及机械效率进行了分析.实验结果表明,SDBD消耗功率、放电强度和诱导气流均会随着激励电压的增大而增大,但机械效率存在先增大后减小的趋势,说明等离子体流动控制中研究中存在最佳效率点.     

聚集态和陷阱对交联聚乙烯真空沿面闪络特性的影响

研究了半结晶聚合物交联聚乙烯的聚集态和陷阱等对真空沿面闪络特性的影响.交联聚乙烯(XLPE)在135℃下恒温10min后,分别经过-56℃,-25℃淬火处理,自然降温,或1℃/min,0.5℃/min慢速降温等热处理过程,测量了热处理后试样的电气性能、显微结构、陷阱分布和真空中的沿面闪络特性.实验结果表明,与未热处理试样相比,热处理试样的直流闪络电压最高提高了76%,脉冲闪络电压最高提高了19%.认为热处理改变了XLPE试样的聚集态和陷阱,从而提高了XLPE试样的真空沿面闪络性能,提出了可以通过控制半结晶聚合物的聚集态和缺陷结构提高其真空沿面闪络性能.     

介质阻挡放电中体放电和沿面放电的光谱线形研究

在放电间隙较大的介质阻挡放电中,利用高速照相机,同时观察到了体放电(VD)和沿面放电(SD)。采用光谱法,研究了VD和SD的光谱线形随放电参数的变化。在氩气介质阻挡放电中,测量了VD和SD的Ar Ⅰ(2P₂→1S₅)谱线展宽和频移随气压及放电间隙的变化。结果发现：SD的展宽和频移均比VD的大,说明SD的电子密度高于VD的电子密度;随着压强从40 kPa增大到60 kPa,VD和SD的谱线展宽及频移均增加,表明它们的电子密度均随压强的增大而升高;随着d值从3.8 mm增大到4.4 mm,VD和SD的谱线展宽也增加,反映它们的电子密度均随d值的增大而增加。     

介质阻挡放电中超四边斑图沿面放电的光谱研究

利用水电极介质阻挡放电装置,在氩气和空气的混合气体中,首次观察到了超四边斑图沿面放电,它是由中心点和暗点组成的。通过观察普通相机的斑图照片,可以发现中心点位于周围四个暗点的中心处。利用高速录像机对斑图进行短曝光拍摄,观察发现中心点对应体放电,暗点对应沿面放电,暗点由这些沿面放电形成。中心点和暗点的亮度有所不同,这说明中心点和暗点的等离子体状态可能不同。采用发射光谱法,研究了超四边斑图沿面放电的的中心点和暗点的等离子体参量随氩气含量的变化趋势。利用氮分子第二正带系(C3Π_u→B3Π_g)发射谱线,计算得出了中心点和暗点的分子振动温度; 然后通过氩原子696.57 nm (2P₂→1S₅)谱线的展宽,研究了中心点和暗点的电子密度。实验结果表明： 在相同氩气含量下,暗点的分子振动温度和电子密度均高于中心点的相应等离子体参量; 在其他实验条件不变的情况下,随着氩气含量从90%增大到99.9%,中心点和暗点的分子振动温度和电子密度均逐渐增大。结果表明中心点和暗点的等离子状态不同,说明二者的放电机制可能不同。     

大面积沿面放电等离子体温度的光谱研究

设计了水电极放电装置,在空气/氩气混合气体中实现了大面积沿面放电。采用发射光谱法,对分子振动温度、电子平均能量和电子激发温度等随气压的变化进行了研究。根据氮分子第二正带系(C3Π_u→B3Π_g)的发射谱线计算出氮分子的振动温度;使用Ar 763.51 nm(2P₆→1S₅)和772.42 nm(2P₂→1S₃)的两条发射谱线的强度比得到电子激发温度;通过氮分子离子391.4 nm和氮分子337.1 nm两条发射谱线的相对强度之比得出了电子的平均能量的变化。实验研究了发射光谱随气压的变化,发现其强度随着气压的增加而增强,且其整个轮廓和谱线强度之比也发生变化。随着气压从0.75×105Pa升高到1×105Pa,分子振动温度、电子激发温度和电子能量均呈下降趋势。     

高压沿面放电烟气脱硫技术动态实验研究

本文针对高压沿面放电活化气体的烟气脱硫技术,在静态实验研究的基础上进行了实验室冷态动态的实验研究。设计了便于反应和测量的动态实验装置。实验解释了电子束法脱硫技术中导致氨气泄漏的部分原因,验证了高压沿面放电脱硫技术可以在较低的运行电压下,达到提高脱硫效率,减少氨气泄漏的作用。     

从单分子到凝聚相水体系的理论描述：势能面和分子动力学最新进展

本文回顾了近十年来水体系的势能面与分子动力学理论研究的最新进展,包括水分子参与的气相反应,固体表面上的吸附与解离动力学,以及从团簇到凝聚相水的结构、振动光谱与统计力学模拟. 近年来再次发展起来的机器学习技术,例如结合置换不变多项式的神经网络,或结合基本不变量的神经网络,已被成熟应用于气相与固体表面体系的高精度势能面构造中. 对于团簇甚至凝聚相水体系,原子中心神经网络方法或基于核的高斯过程方法应用更为广泛. 此外,在多体展开框架下,在气相体系中发展起来的的方法也组成了高维度体系势函数构造的高精度方案. 当前凝聚相水体系面临的主要问题是高精度从头算数据集的积累,兼顾计算精度与效率的双杂化密度泛函是一种可能的解决方案. 在动力学理论方面,无论是化学反应截面计算还是振动光谱模拟,往往需要合理描述水分子中氢原子的量子效应,才能得到较为可靠的理论计算结果. 量子波包动力学方法已经在气相反应机理研究方面有深入的应用,也在包含数个水分子的团簇振动分析中有初步应用. 基于路径积分的分子动力学方法正在较大水团簇以及凝聚相水的结构与谱学模拟方面发挥重要作用.     

光谱学方法研究介质阻挡沿面放电辉光模式的电场分布

利用介质阻挡沿面放电装置,在低气压空气中实现了辉光放电模式。利用光电倍增管对放电发光信号进行检测,发现外加电压每半周期出现一个发光脉冲,并且正负半周期的光脉冲是不对称的。利用Photoshop软件处理放电的照片,研究发现平行于高压电极不同位置的发光强度基本相同,然而距离高压电极越远,发光强度减小。放电中总电场由外加电场和电介质积累的壁电荷电场共同决定,确定该电场具有重要意义。通过分析放电的发射光谱中N+₂(B 2Σ+_u→X 2Σ+_g)谱线391.4 nm和N₂的第二正带系(C 3Π_u→B 3Π_g)谱线337.1 nm的比值,可以定性地说明电场的分布。研究发现电场在高压电极附近较大而远离高压电极处较小。这些研究结果对沿面放电的数值模拟和工业应用具有重要的价值。     

强外电场作用下BN分子的结构与激发特性

采用密度泛函理论的B3LYP方法在6-311++g(d.p)水平上优化得到了BN分子轴向加不同外电场时的基态结构参数,包括键长、电偶极矩、电荷分布、前线轨道、红外光谱.计算结果表明,随着正向电场增加,分子结构参数与外电场强度有明显关联,并呈现不对称性.另外,在同样的基组下利用合时密度泛函理论方法研究了外电场对BN分子激发能和振子强度的影响.结果表明,电子跃迁光谱随正向电压的增加而呈现蓝移现象,但振子的强度与电场关联较为复杂,说明光谱强度易受外电场影响.     

强外电场作用下BF分子结构和激发特性

采用密度泛函(DFT)方法LSDA在6-311++G(d,p)基组水平上优化得到了分子轴方向不同电场(-0.03～0.05a.u.)作用下,BF分子的基态结构参数、电偶极矩μ、电荷分布、HOMO能级、LUMO能级等。在优化构型下,用同样的基组采用杂化CIS-DFT方法(CIS-LSDA)研究了同样外电场条件下对BF分子的激发能和振子强度的影响。结果表明:随着电场的增加,分子结构与外电场有着强烈的依赖关系,且对电场方向的依赖呈现非对称性。分子总能量先增大后减小,电偶极矩μ先增大,后减小,最后不断增大。电场对振子强度的影响比较复杂,有的增大有的减小,表明电子跃迁光谱强度受外场影响。     

分子构型对分子器件伏-安特性的影响

本文选取4,4′-二巯基联苯分子通过终端S原子化学吸附于两Au原子团簇形成分子结,利用从头计算方法和弹性散射格林函数理论研究了该分子两苯环之间不同位置取向对分子能级结构以及该分子结伏安特性的影响.计算结果表明苯环扭转角增加会使分子能级发生不同程度的移动,从而引起最高占据轨道(HOMO)与最低未占据轨道(LUMO)的间距增大.扭转角增大也会导致分子轨道的扩展性变差,从而使体系的导电性能降低.当扭转角为90度时,体系的导电性能最差.该工作有利于未来分子电子学器件的设计.     

Theoretical study on the relationship between the position of the substituent and the ESIPT fluorescence characteristic of HPIP

The influences of the substituent base position on the excited state intramolecular proton transfer fluorescence properties were explored in 2-(2'-hydroxyphenyl)imidazo[1,2-a]-pyridine(HPIP)and HPIP's derivatives(5'Br-HPIP and 6'BrHPIP).And the density functional theory(DFT)and time-dependent DFT(TD-DFT)methods were used to calculate the molecule structures.The calculated results showed that the influence of 5'Br-HPIP on the fluorescence intensity is stronger than that of 6'Br-HPIP.The fluorescence emission peak of 5'Br-HPIP occurred a blue shift compared with HPIP,and 6'BrHPIP exhibited an opposite red shift.The change of the fluorescence emission peak was attributed to the decrease of the energy gap from 6'Br-HPIP to 5'Br-HPIP.Our work on the substituent position influence could be helpful to design and develop new materials.     

Surface rumpling of cubic CaTiO3 from density functional theory

In this paper, the structure of cubic CaTiO3 （001） surfaces with CaO and TiO2 terminations has been studied from density functional calculations. It has been found that the Ca atom has the largest relaxation for both kinds of terminations, and the rumpling of the CaO-terminated surface is much larger than that of TiO2-terminated surface. Also we have found that the metal atom relaxes much more prominently than the O atom does in each layer. The CaO-terminated surface is slightly more energetically favourahle than the TiO2-terminated surface from the analysis of the calculated surface energy.     

经式8-羟基喹啉铝的光谱与激发性质密度泛函

经式8-羟基喹啉铝(mer-Alq3)是一种光电性能优良的小分子有机半导体发光材料.本文采用密度泛函理论(DFT)B3LYP/6-31G*方法和基组对其进行结构优化,计算并研究了该分子的红外光谱、拉曼光谱和前线轨道.计算得到的红外光谱、拉曼光谱均与实验相符.前线轨道表明基态最高占据轨道(HOMO)的电子云主要集中在苯酚环,最低未占据轨道(LUMO)的电子云主要集中在吡啶环.用含时密度泛函理论(TDDFT)计算得到紫外-可见吸收光谱,采用空穴-电子分析法研究了电子激发特征.结果表明:电子从基态到激发态的跃迁,主要是8-羟基喹啉环内或环间的电荷转移,以π-π*跃迁为主,包括局域激发和电荷转移激发两种类型.本工作对mer-Alq3分子发光机理提出更深入的认识,能为进一步提高该分子发光效率和调控分子的发光范围提供一定的理论指导.     

Theoretical investigation on the excited state intramolecular proton coupled charge transfer phenomenon for a novel fluorophore

We theoretically investigate the excited state behaviors of the novel fluorophore tetraphenylethene‐2‐(2′‐hydroxyphenyl)benzothiazole (TPE‐HBT), which was designed based on the intersection of TPE and HBT, using density functional theory and time‐dependent density functional theory methods. Compared with previous experimental results about fluorescence peaks, our calculated results are in good agreement with experimental data, which further confirms that the theoretical level we used is reasonable. Furthermore, our results confirm that the excited state intramolecular proton transfer (ESIPT) process happens upon photoexcitation, which is distinctly monitored by the infrared spectra and the potential energy curves. In addition, the calculation of highest occupied molecular orbital and lowest unoccupied molecular orbital reveals that the electron density change of proton acceptor because of the intramolecular charge transfer (ICT) process in the S₁ state induces the ESIPT. Moreover, the transition density matrix is worked out to facilitate deeper insight into the ESIPT coupled ICT process. It is hoped that the present work not only elaborates the ESIPT coupled ICT phenomenon and corresponding mechanisms for the TPE‐HBT but also may be helpful to design and develop new materials and applications involved in TPE‐HBT systems in future.     

First principles study on the charge density and the bulk modulus of the transition metals and their carbides and nitrides

A first principles study of the electronic properties and bulk modulus （B0） of the fcc and bcc transition metals, transition metal carbides and nitrides is presented. The calculations were performed by plane-wave pseudopotential method in the framework of the density functional theory with local density approximation. The density of states and the valence charge densities of these solids are plotted. The results show that B0 does not vary monotonically when the number of the valence d electrons increases. B0 reaches a maximum and then decreases for each of the four sorts of solids. It is related to the occupation of the bonding and anti-bonding states in the solid. The value of the valence charge density at the midpoint between the two nearest metal atoms tends to be proportional to B0.     

Surface properties of 3d transition metals

Using the projector augmented wave method within density functional theory, we present a systematic study of the layer relaxation, surface energy and surface stress of 3d transition metals. Comparing the calculated trends for the surface energy and stress with those obtained for 4d and 5d metals we find that magnetism has a significant effect on the surface properties. Enhanced surface magnetic moments decrease the size of the surface relaxation, lower the surface energy and surface stress, leading to compressive stress in Cr and Mn.     

Influence of intramolecular hydrogen bond formation sites on fluorescence mechanism

The fluorescence mechanism of HBT-HBZ is investigated in this work. A fluorescent probe is used to detect HClO content in living cells and tap water, and its structure after oxidation by HClO (HBT-ClO) is discussed based on the density functional theory (DFT) and time-dependent density functional theory (TDDFT). At the same time, the influence of the probe conformation and the proton transfer site within the excited state molecule on the fluorescence mechanism are revealed. Combined with infrared vibrational spectra and atoms-in-molecules theory, the strength of intramolecular hydrogen bonds in HBT-HBZ and HBT-ClO and their isomers are demonstrated qualitatively. The relationship between the strength of intramolecular hydrogen bonds and dipole moments is discussed. The potential energy curves demonstrate the feasibility of intramolecular proton transfer. The weak fluorescence phenomenon of HBT-HBZ in solution is quantitatively explained by analyzing the frontier molecular orbital and hole electron caused by charge separation. Moreover, when strong cyan fluorescence occurs in solution, the corresponding molecular structure should be HBT-ClO(T). The influence of the intramolecular hydrogen bond formation site on the molecule as a whole is also investigated by electrostatic potential analysis.     

分子超激发态结构的理论研究：F2离子对解离效率谱研究

在量子数亏损理论框架下,利用多重散射自洽场方法和Feynman传播子算法研究了高分辨的F2分子超激发态结构;该超激发态能够解离为正负离子对F+(3P2,1,0)+F-(1S0).理论分析能够清楚地标识其振动分辨谱,并很好地与实验测量符合.文章还阐述了发展分子超激发态结构研究的前景.     

First Principles Study of Half Metallic Properties of VSb Surface and VSb/GaSb (001) Interface

The structural, electronic, and magnetic properties of VSb in zincblende, andNiAs phases, VSb (001) film surfaces and its interfaces with GaSb (001) havebeen investigated within the framework of the density functional theoryusing the FPLAPW+lo approach. The NiAs structure is more stable than the ZB phase, ZB VSb is found to a half-metallic ferromagnetic. The V-terminated surfaces retain the half-metallic character, while the half-metallicity is destroyed for Sb-terminated surfaces due to surface states, which originate from p electrons. The phase diagram obtained through the ab-initio atomisticthermodynamics shows that the formation energy of ZB VSb is about 0.1 Ryd.The half-metallicity character is also preserved at VSb/GaSb (001) interface.The conduction band minimum (CBM) of VSb in the minority spin case liesabout 0.47 eV above that of GaSb, suggesting that the majority spin can beinjected into GaSb without being flipped to the conduction bands of the minority spin.