乙基苯胺的转动光谱及分子结构

本文使用傅里叶变换微波谱仪研究了乙基苯胺类物质(邻乙基苯胺，间乙基苯胺，对乙基苯胺)的分子结构. 由于此类分子含氮原子(I¹⁴N=1)，因此跃迁谱线中都呈现出核四级裂分. 通过比较实验测定得到的分子结构，可总结苯胺环上不同位置乙基的取代对氨基及分子整体结构的影响.     

乙基苯胺的转动光谱及分子结构（英文）

本文使用傅里叶变换微波谱仪研究了乙基苯胺类物质(邻乙基苯胺,间乙基苯胺,对乙基苯胺)的分子结构.由于此类分子含氮原子(I~(14)N=1),因此跃迁谱线中都呈现出核四级裂分.通过比较实验测定得到的分子结构,可总结苯胺环上不同位置乙基的取代对氨基及分子整体结构的影响.     

芴酮及苯并噻二唑取代的低聚芴环光学特性的理论研究

从链形态、热振动及共轭特性等方面系统的研究了芴酮及苯并噻二唑取代的低聚芴环引起的光学性质的变化. 采用从头算和含时密度泛函方法计算了模型体系的垂直吸收光谱和包含振动结构的吸收和发射光谱. 通过合理的考虑低聚芴环间扭转模式的非谐性效应,理论光谱和实验光谱得到了很好的吻合. 芴链上掺杂的芴酮和苯并噻二唑均具有电子捕获特性,使得整个分子的吸收带变宽且发射光谱红移,从而起到了调制纯芴链发光特性的作用. 当温度升高时,芴酮掺杂的低聚芴的光谱谱型会变得复杂,含有更多的振动结构. 苯并噻二唑掺杂的低聚芴的光谱线型始终比较光滑,几乎没有振动结构,这是因为在低频模式在苯并噻二唑环上很难找到共振. 苯并噻二唑掺杂的低聚芴的激发态势能面更平缓,这有利于增强电子的离域,从而得到更大的光谱红移.     

硼、氮原子的掺杂对单个苯环的电子结构与传输特性的影响

采用基于密度泛涵理论的第一性原理和非平衡格林函数方法研究了硼、氮原子的掺杂对于苯环的电子结构与电子传输特性的影响.结果显示硼、氮原子的掺杂明显改变了C_(32)分子的电子结构和电子传输特性,硼原子的掺杂明显增强了苯环的电子传输特性,而氮原子的掺杂却明显降低了苯环的电子传输特性.同时分析了产生这些现象的原因.计算结果还显示随着外加偏压的增大,苯环的电子传输性能逐渐减弱.     

并苯纳米环[6]CA及其衍生物的电子结构和光物理性质的密度泛函理论研究

采用密度泛函理论PBE0方法在6-31G(d, p) 基组水平上对比研究并六苯纳米环[6]CA及BN取代纳米环[6]CA-BN的几何结构及电子性质. 同时探讨锂离子掺杂对不同体系的芳香性、前线分子轨道、电子吸收光谱及传输性质的影响. 通过电离势、亲合势及重组能的计算, 预测纳米环体系得失电子的能力及传输性能. 结果表明:[6]CA的能隙很小, BN取代后, 能隙明显增大; 锂离子掺杂到两种纳米环中, 在不明显改变前线分子轨道分布的前提下, 几乎同步降低了最高占据轨道、 最低未占据轨道能级, 锂离子掺杂使载流子传输性能得到很大改善; 电子吸收光谱拟合发现, BN取代使吸收光谱很大程度蓝移, 吸收强度明显减小; 而锂离子掺杂对光谱的强度及吸收范围没有明显影响. 关键词： 碳纳米环 硼氮纳米环 锂离子掺杂 密度泛函理论     

硼、氮原子的掺杂对单个苯环的电子结构与传输特性的影响

采用基于密度泛涵理论的第一性原理和非平衡格林函数方法研究了硼、氮原子的掺杂对于苯环的电子结构与电子传输特性的影响．结果显示硼、氮原子的掺杂明显改变了C32分子的电子结构和电子传输特性特性,硼原子的掺杂明显增强了苯环的电子传输特性,而氮原子的掺杂却明显降低了苯环的电子传输特性．同时分析了产生这些现象的原因．计算结果还显示随着外加偏压的增大,苯环的电子传输性能逐渐减弱．     

Mg和Zn掺杂CuAlS2电子结构的分析

从能带结构和态密度分析了黄铜矿CuAlS₂的电子结构.对比未掺杂CuAlS₂,从晶体结构、电子结构、电荷密度分布讨论了Mg和Zn替位Al掺杂对CuAlS₂的影响.结果表明:Mg和Zn掺杂CuAlS₂都导致晶格常数增大,Mg掺杂晶胞体积增大更多;掺杂在价带顶引入受主态,形成p型电导;Mg掺杂比Zn掺杂的受主能级电离能略小;而Zn掺杂CuAlS₂体系总能更低,晶格结构更稳定. 关键词： 2')" href="#">CuAlS₂ p型掺杂 电子结构 能带结构     

光致分子间电子转移-受体分子结构对转移速率的影响

本文利用超快时间分辨瞬态光栅光谱技术研究了受体分子结构对光致分子间电子转移速率的影响,以罗丹明101和罗丹明6G在苯胺中的溶液作为研究样品. 苯胺到两种染料分子之间的前向电子转移时间常数以及后续的从染料分子到苯胺的反向电子转移时间常数可以被测得. 结果表明无论是前向电子转移还是反向电子转移,罗丹明6G都较罗丹明101进行得更快. 通过量子化学计算以及后续分析,发现更具柔性的罗丹明6G分子和苯胺之间具有更强的分子间电子耦合从而导致更大的分子间电子转移速率.     

光致分子间电子转移-受体分子结构对转移速率的影响（英文）

本文利用超快时间分辨瞬态光栅光谱技术研究了受体分子结构对光致分子间电子转移速率的影响,以罗丹明101和罗丹明6G在苯胺中的溶液作为研究样品.苯胺到两种染料分子之间的前向电子转移时间常数以及后续的从染料分子到苯胺的反向电子转移时间常数可以被测得.结果表明无论是前向电子转移还是反向电子转移,罗丹明6G都较罗丹明101进行得更快.通过量子化学计算以及后续分析,发现更具柔性的罗丹明6G分子和苯胺之间具有更强的分子间电子耦合从而导致更大的分子间电子转移速率.     

一维螺旋型Se原子链中的Rashba效应和平带性质

探索低维体系电子态的调控规律可以为构筑下一代微纳电子学器件提供理论基础.本文采用第一性原理计算研究了一维螺旋型Se原子链的结构性质和电子性质.结果发现,该结构比直线型结构能量要低得多,且具有动力学和热力学稳定性.能带计算表明,这种螺旋型一维原子链结构是带隙约为2.0 eV的半导体,且在X点附近展现出Rashba型的自旋劈裂.这种特殊的原子链结构便于人们通过应力调控其电子性质.计算结果表明, 5%的拉伸应变就可以将其带隙减小20%,而5%的压缩应变将Rashba能量偏移增大到平衡体积时的2倍多.此外,其价带是一条平带,引入空穴掺杂可以诱导产生磁性,从而使体系转变为半金属.进一步增加空穴掺杂,体系转变为铁磁金属.同样,这种掺杂效应还出现在一维螺旋型Te原子链中.     

La,Ce,Nd掺杂对单层MoS_2电子结构的影响

为了研究稀土掺杂对单层MoS2电子结构的影响,文章基于密度泛函理论框架下的第一性原理,采用平面波赝势方法分别计算了本征及La,Ce,Nd掺杂单层MoS2的晶格参数、能带结构、态密度和差分电荷密度.计算发现,稀土掺杂所引起的晶格畸变与杂质原子的共价半径大小有关,La杂质附近的键长变化最大,Nd杂质附近的键长变化最小.能带结构分析表明,La掺杂可以在MoS2的禁带中引入3个能级,Ce掺杂可以形成6个新能级,Nd掺杂可以形成4个能级,并对杂质能级属性进行了初步分析.差分电荷密度分布显示,稀土掺杂可以使单层MoS2中的电子分布发生改变,尤其是f电子的存在会使差分电荷密度呈现出反差极大的物理图象.     

Electrical conductivity of individual polypyrrole microtube

Conducting microtubes (0.4－0.5μm in outer diameter) made of polypyrrole (PPy) doped with p-toluene sulfonic acid (PTSA) were synthesized by a self-assembly method. We report the electrical conductivity of an individual PPy microtube, on which a pair of platinum micro-leads was fabricated by focused ion beam deposition. The measured room-temperature conductivity of the individual PPy microtube was 0.29S/cm, which is comparable to that of template-synthesized PPy micro/nanotubes. The temperature dependence of conductivity of the individual microtube follows the three-dimensional variable-range hopping (3D VRH) model.     

Structural stability and electronic properties of Ni-doped armchair graphene nanoribbons

The size dependent electronic properties of armchair graphene nanoribbons (AGNR) with Ni doped atoms have been investigated using spin-unrestricted density functional theory. We predict antiferromagnetic (AFM) ground states for Ni-termination and one edge Ni-doping. The computed formation energy reveals that one edge Ni-terminated AGNR are energetically more favourable as compared to pristine ribbons. One edge substitutional doping is energetically more favourable as compared to centre doping by ∼1 eV whereas both edge doping is unfavourable. The bond length of substitutional Ni atoms is shorter than that of Ni adsorption in GNR, implying a stronger binding for substitutional Ni atoms. It is evident that binding energy is also affected by the coordination number of the foreign atom. The results show that Ni-interaction perturbs the electronic structure of the ribbons significantly, causing enhanced metallicity for all configurations irrespective of doping site. The band structures reveal the separation of spin up and down electronic states indicating towards the existence of spin polarized current in Ni-terminated and one edge doped ribbons. Our calculation predicts that AGNR containing Ni impurities can play an important role for the fabrication of spin filters and spintronic devices.     

剪切形变下掺杂及缺陷对MoS2电子结构的影响

本文利用密度泛函理论,研究剪切形变下掺杂改性及不同类型缺陷对MoS2电子结构的影响。发现：剪切形变下,MoS2+P体系为相对最稳定的结构,掺杂改性相较于缺陷对模型稳定性影响更小;模型MoS2+P+Se中P-Mo键易形成共价键,而其中的Se-Mo键和MoS2+P-Mo-S模型中的P-Mo键,易形成离子键;掺杂使MoS2模型能隙变大,而缺陷使能隙减小,且S和Mo原子共缺陷的模型带隙为0;缺陷相较于掺杂改性模型,更能使Mo原子周围增加电荷聚集度,带隙值更低,更能影响或调控模型的电子结构。     

Pt-N共掺杂锐钛矿TiO_2的第一性原理研究

采用基于密度泛函理论(DFT)的第一性原理中的平面波超软赝势(PWPP)方法对理想TiO_2,N单掺杂,Pt单掺杂和Pt-N共掺杂锐钛矿相TiO_2的电子结构进行计算,分析N单掺杂、Pt单掺杂及Pt-N共掺杂对锐钛矿相TiO_2的晶体结构、能带和态密度的影响.计算结果表明:掺杂后TiO_2的晶格发生畸变,原子间键长的变化使晶格发生膨胀,Pt单掺杂、N单掺杂TiO_2禁带宽度变窄,Pt-N共掺杂TiO_2分别在价带顶和导带底产生杂质能级,且禁带宽度缩小范围大,表明Pt-N共掺杂能进一步提高锐钛矿TiO_2催化性能.     

用GGA+U法研究稀土掺杂对ZnO电子结构磁性和光学性质的影响

基于自旋密度泛函理论框架下的广义梯度近似平面波模守恒赝势方法,确定了准确计算Zn_(16)O_(16)超晶胞各原子对应的U值;通过计算形成能和化学键的布局分析了掺杂结构的稳定性;通过原子电荷布局和自旋电子态密度的计算分析了掺杂结构的能带结构和磁性状态;讨论了各稀土原子掺杂对ZnO吸收光谱的影响.结果表明:稀土元素的引入使晶格膨胀,Zn-O键最长键增大而最小键减小,导致氧四面体畸变;Y/La/Ce掺杂的ZnO具有亚铁磁性,Th掺杂ZnO则呈弱铁磁性,Ac掺杂ZnO为顺磁体;稀土元素使ZnO的价带和导带下移,费米能级进入导带,增强了体系的电导率;Y/La/Ac掺杂对ZnO带隙宽度的影响较小,吸收光谱略微蓝移,而Ce/Th掺杂则有效提升了ZnO对可见光的吸收.     

Cobalt nanoparticles doped emaraldine salt of polyaniline: A promising room temperature magnetic semiconductor

Incorporation of magnetic nanoparticles in polymers with organic functional groups working as semiconducting substrate is of immense interest in the field of dilute magnetic semiconductors (DMS) and spintronics. In this article we report on synthesis and evaluation of dilutely doped (0-10 wt%) cobalt nanoparticles in emaraldine salt (ES) of polyaniline in the presence of dodecyl benzene sulfonic acid (DBSA) and p-toluene sulfonic acid (p-TSA) using a sonochemical-assisted-reduction approach as a possible DMS candidate. The X-ray diffraction pattern and high resolution transmission electron microscopy (HRTEM) image show the ES to be polycrystalline, in which 10 nm sized Co nanoparticles get embedded in its FCC structural form. From Fourier transform infrared (FT-IR) and UV-visible (UV-vis) spectroscopy studies, it is predicted that cobalt particles get electrostatically bound to the specific ion sites of ES, thereby modifying torsional degrees of freedom of the system. The applied field dependent magnetization study shows that the sample exhibits hysteresis loop with a minimal doping of 3 wt% of Co nanoparticles and increases with the amount of Co nanoparticles in ES due to dipolar interaction. The electron transport data show that with increase in Co wt% there is a gradual shift from ohmic to non-ohmic response to the sample bias, accompanied by opening of electrical hysteresis and an increased resistance. The non-linear response of higher doped systems has been attributed to the combination of direct and Fowler-Nordheim tunneling phenomena in these systems. Persistence of optical and transport properties of the polymer, with an introduction of magnetic moment in the system, envisages the system to be a fine magnetic semiconductor.     

Molecular dynamic simulations of elastomer structure and its influence on anisotropic stress under time-varying strain

We investigate the evolution of polymer structure and its influence on uniaxial anisotropic stress under time-varying uniaxial strain, and the role of external control variables such as temperature, strain rate, chain length, and density, using molecular dynamics simulation. At temperatures higher than glass transition, stress anisotropy in the system is reduced even though the bond stretch is greater at higher temperatures. There is a significant increase in the stress level with increasing density. At higher densities, the uncoiling of the chains is suppressed and the major contribution to the deformation is by internal deformation of the chains. At faster rates of loading stress anisotropy increases. The deformation mechanism is mostly due to bond stretch and bond bending rather than overall shape and size. Stress levels increase with longer chain length. There is a critical value of the functionality of the cross-linkers beyond which the uniaxial stress developed increases caused primarily by bond stretching due to increased constraint on the motion of the monomers. Stacking of the chains in the system also plays a dominant role in the behaviour in terms of excluded volume interactions. Low density, high temperature, low values of functionality of cross-linkers, and short chain length facilitate chain uncoiling and chain slipping in cross-linked polymers.     

Suppression of Jahn-Teller distortion by chromium and magnesium doping in spinel LiMn2O4: A first-principles study using GGA and GGA+U

The effect of doping spinel LiMn₂O₄ with chromium and magnesium has been studied using the first-principles spin density functional theory (DFT) within generalized gradient approximation (GGA ) and GGA+U. We find that GGA and GGA+U give different ground states for pristine LiMn₂O₄ and same ground state for doped systems. For LiMn₂O₄, the body-centered tetragonal phase was found to be the ground-state structure using GGA and face-centered orthorhombic using GGA+U, while for LiM_0.5Mn_1.5O₄ (MCr or Mg) it was base-centered monoclinic and for LiMMnO₄ (MCr or Mg) it was body-centered orthorhombic in both GGA and GGA+U. We find that GGA predicts the pristine LiMn₂O₄ to be metallic while GGA+U predicts it to be insulating, which is in accordance with the experimental observations. For doped spinels, GGA predicts the ground state to be half metallic while GGA+U predicts it to be insulating or metallic depending on the doping concentration. GGA+U predicts insulator-metal-insulator transition as a function of doping in case of Cr and in case of Mg the ground state is found to go from insulating to a half metallic state as a function of doping. Analysis of the charge density and the density of states (DOS) suggest a charge transfer from the dopants to the neighboring oxygen atoms and manganese atoms. We have calculated the Jahn-Teller active mode displacement Q₃ for doped compounds using GGA and GGA+U. The bond lengths calculated from GGA+U are found to be in better agreement with experimental bond lengths. Based on the bond lengths of metal and oxygen, we have also estimated the average oxidation states of the dopants.     

Electron localization length in polyaniline

Electrical DC conductivity, magnetic susceptibility, and EPR measurements are used to investigate the electron localization behavior of polyaniline as a function of the dopant type using seven sulfonic acid based doping acids. In spite of differences in the magnitude and the temperature dependences of DC conductivity and magnetic susceptibility data, the experiments reveal a localization length of approximately 30 Å for all the samples. We conclude that this result is essentially due to disorder in the basic morphological structure of a polymer that seems to be determined, among other factors, by the nature of the monomeric units comprising the polymer chains.