氧原子对向列相液晶粘度的影响

对于向列液晶分子中常见的典型含氧基团,通过密度泛函理论(Density Functional Theory,DFT)的B3LYP/6-31G(d)方法计算了氧原子处于不同位置以及与不同基团相连时的静电势分布和偶极矩大小,分析了含氟基团和氧原子相连时对静电势分布和偶极矩的影响,研究了这些含有氧原子的基团和其它相关基团对应的液晶化合物的粘度与静电势分布和偶极矩的联系,所得到的结论有助于理解液晶粘度与分子电子结构之间的关系以及低粘度液晶的分子设计.     

四方晶相HfO2电子结构和光学性质研究

采用密度泛函理论(DFT)框架下的局域密度近似(LDA),计算了四方HfO2晶体的电子结构,包括能带结构和态密度.在此基础上计算了四方Hf02晶体的光学线性响应函数,包括复介电函数、吸收光谱、复折射率和光电导谱.通过比较发现,计算结果与实验结果吻合较好,说明采用密度泛函理论的局域密度近似来计算HfO2材料的光学性质是比较可靠的.     

纤锌矿GaN光电性质的第一性原理研究

利用平面渡赝势密度泛函的方法,结合广义梯度近似,对纤锌矿GaN的光电性质进行了研究.对纤锌矿GaN的能带结构、态密度分布、复介电函数和吸收光谱进行了计算.文中分析了纤锌矿结构GaN晶体可能的跃迁及其对应的吸收光谱.结果显示GaN晶体的光学性质与晶体的电子结构直接相关.计算结果为进一步理解和改进纤锌矿GaN的光电性质提供理论基础.     

缺陷对石墨烯电子结构的影响

基于第一性原理计算方法,通过密度泛函理论（DFT）和广义梯度近似（GGA）对本征及含有缺陷的石墨烯超晶胞进行了电子结构的计算,研究了多种缺陷对石墨烯电子结构的影响。研究发现,多种缺陷均使石墨烯能带在费米能级附近出现缺陷态对应的能带,并导致其能隙有不同程度的增大,而且与之对应的态密度也随之发生相应的变化。其中,Stone...     

一种新型半导体材料的电子结构和光学特性：石墨烯一氧化物：

本文首次基于密度泛函理论研究了石墨烯一氧化物一种新型半导体材料的电子结构和光学特性。计算表明石墨烯一氧化物是直接带隙为0.95ev的半导体。通过绘制态密度和分波态密度研究了该材料的能带结构。除此之外,本文给出了该材料的光学特性,这对于材料在光电子器件的潜在应用有着一定的意义。     

GaAs第一性原理研究

为了深入认识GaAs的电子结构和光学性质,计算和分析了GaAs晶体的能带结构、电子态密度、分渡态密度、光学常数,所有计算都是基于密度泛函理论(DFT)框架下的第一性原理平面渡赝势方法.研究证明,其具有广泛的应用领域.     

(111)方向的InAs/GaSb超晶格材料电子结构的杂化泛函计算

采用电子密度泛函理论方法计算了一系列（111）方向的InAs/GaSb超晶格的电子结构和能带结构。将杂化泛函的计算结果与普通密度泛函方法的计算结果进行了比较。Heyd-Scuseria-Ernzerhof (HSE)杂化与对固体修正的Perdew-Burke-Ernzerhof (PBE)近似结合的杂化泛函显示了较传统PBE方法和若干其他杂化泛函更符合实验数据的结果。采用该方法研究了InAs/GaSb超晶格的带隙随超晶格周期厚度以及InAs/GaSb比例变化的规律。其结果与以往实验结果符合很好。这些结果表明HSE-PBEsol方法对于估计InAs/GaSb超晶格的电子性质适用。     

温度诱导CL-20相变的太赫兹光谱特性

2,4,6,8,10,12-六硝基-2,4,6,8,10,12-六氮杂异伍兹烷（HNIW, CL-20）是一种具有笼形结构的高能化合物，在军事及民用领域具有广阔的应用前景。为了深入理解CL-20晶体相变物理机制，采用太赫兹时域光谱技术（THz-TDS）对23.0~179.8 ℃升温范围内的吸收光谱进行了研究。热作用下太赫兹光谱的显著变化表明136.8 ℃时CL-20开始发生不可逆相变，结合固态密度泛函理论（DFT）计算鉴别该转变为ε→γ相变。并且，对CL-20低频振动特性的分析表明，分子笼型骨架的振动模态在相变中发生了显著改变，分子间广泛的范德华相互作用是其重要来源。此外，骨架外硝基基团的旋转振动演变与分子的氢键作用密切相关。该研究为进一步理解CL-20在高温加载下发生相变乃至爆轰/爆燃过程中的复杂物理机制提供了参考，对新型CL-20基优质炸药的设计和合成具有重要意义。     

两种新型芴类衍生物的三光子吸收特性研究

为了研究分子结构对三光子吸收的影响,合成了两种新型芴类衍生物,分别是2,7-二（2-4（甲氧基苯基）乙炔基）-9,9-二辛基-9H-芴（A）和2-溴-7-（2-（4-甲氧基苯基）乙炔基）-9,9-二辛基-9H-芴（B）,采用1064nm的Nd∶YAG激光器测试其三光子吸收截面的方法,得到了它们的三光子吸收截面分别高达（6.03±0.6）×10-76cm6·s2/photon2和（4.25±0.4）×10-76cm6·s2/photon2的结果,在高斯03软件下,用密度泛函方法对这两个分子进行了结构优化,并用含时密度泛函理论计算了它们的激发态能量和电子轨道。结果表明,分子内电荷转移方向对三光子吸收存在影响。     

La/N共掺Ba5Nb4O15的光电性能的第一性原理研究

采用密度泛函理论（DFT）第一性原理方法研究了La/N共掺对二维钙钛矿Ba5Nb4O15的电子结构、光吸收系数和迁移率的调制作用。计算结果表明,在所选择的掺杂浓度下,La/N共掺使其带隙减小了1.46eV,且仍保持直接带隙,价带顶和导带底都在Γ点。同时,由于掺杂后引入杂质能级使带隙减小,吸收光谱出现明显的红移,可见光区域的光吸收系数显著增大,可有效提高对太阳光的利用率。另外,掺杂后电子和空穴的有效质量显著减小,迁移率提高3～5倍,进一步增强了材料的光电与光催化性能。     

Spray deposited ZnO and Ga doped ZnO based DSSC with bromophenol blue dye as sensitizer: Efficiency analysis through DFT approach

Dye sensitized solar cells based on spray deposited ZnO and Ga doped ZnO (GZO) thin film were fabricated with Bromophenol Blue as the photo sensitizer. XRD results show the hexagonal wurtzite phase of ZnO and GZO thin films with c-axis growth orientation, and the diminished crystalline nature of GZO thin film as the effect of doping. FE-SEM results revealed the morphology induced internal light interaction capability of GZO thin film for better harvesting of photon energy. Photovoltaic studies showed that the DSSC fabricated with GZO thin film has obtained enhanced power conversion efficiency (1%) than the ZnO thin film based DSSC (0.2%), as a result of Ga doping. To investigate the obtained photovoltaic performance of the device, the electronic properties of Bromophenol Blue dye were theoretically analyzed with Density Functional Theory (DFT) study.     

Significant improvement of phenothiazine organic dye-sensitized solar cell performance using dithiafulvenyl unit as additional donor

The simple D-π-A phenothiazine organic dye (C₆PTZ) was modified by introducing excellent electron donor dithiafulvenyl unit with alkyl chains as additional donor to form novel D-D-π-A organic dyes WD14 and WD15 for the first time. These organic dyes were successfully applied in dye-sensitized solar cells and the photovoltaic properties were investigated. Compared with the reference dye C₆PTZ, the power conversion efficiencies increased significantly from 4.16% to 5.87% (WD14) and 6.63% (WD15). The performance improvement is due to the following advantages of the introduction of dithiafulvenyl unit with alkyl chains. Firstly, the light-harvesting capability is improved by increasing electron-donating ability. Secondly, it leads to more efficient inhibition of aggregation between dye molecules. Thirdly, the charge recombination between photoelectrons injected into the conduction band of TiO₂ and the oxidized form $\left({{\text{I}}_3}^{-}\right)$ of the redox couple is restricted due to the double blocking effect originating from the long hexyl chains of the dithiafulvenyl unit and hexyl side chain attached to phenothiazine unit. This work indicates that the incorporation of dithiafulvenyl unit into the simple phenothiazine organic dye greatly improves the solar cell performance, and it will be an effective approach to develop high-performance metal-free organic dyes.     

葡萄糖与果糖太赫兹吸收谱仿真计算

利用Gaussian软件,选取密度泛函理论(DFT)、哈特里—福克理论(HF)对葡萄糖、果糖的单分子在0～3 THz波段的吸收谱进行仿真计算,并与参考文献中的实验结果进行比对。仿真计算结果验证了利用Gaussian软件进行单分子吸收谱计算的可行性。最后基于密度泛函理论得到的结果分析了不同位置吸收峰对应的分子内振动模式。     

Twisted donor substituted simple thiophene dyes retard the dye aggregation and charge recombination in dye-sensitized solar cells

Two novel thiophene 3,4-disubstituted organic dyes with double acceptors at 2,5-position framework photosensitizers were carefully designed and synthesized for the dye sensitized solar cell (DSSC) application. In this submission, the influence of carbazole (Cz) and triphenylaime (NPh3) units substitution at 3,4-position of thiophene is studied. Both the planar structure of carbazole based dyes and three dimension structure of triphenylamine based dyes are found to effectively inhibit the I⁻/I₃⁻ and Co⁺²/Co⁺³ electrolyte on TiO₂ surface. The results show that varying the donor position in dyes also effectively works for DSSC application, even if it does not broaden the absorption peak in visible region (for both the dyes) due to the blocking of electron delocalization at 2,5-positions by acceptor units. With two twisted donors at 3,4-position in Cz-Th-Dye, NPh3-Th-Dye the dye aggregation and charge recombination retarded. The optical, electrochemical, density functional theory and TRPL studies were used to estimate the photovoltaic properties of the dyes. The dye having two acceptors on both sides (2,5-position) of thiophene moiety showed efficient electron extraction from the electron donor part. Without using any additives, Cz-Th dye and NPh3-Th dye in presence of cobalt (II/III) redox shuttle, resulted in the power conversion efficiency (η, PCE) of ∼3.4% and 3.1% respectively. By replacing one acceptor with any other donor, these thiophene moiety can effectively work as a new π-spacer in DSSC application.     

有机半导体Butyl-PBD的DFT理论计算研究

采用密度泛函理论(DFT)方法对2-(4-叔丁苯基)-5-(4-联苯基)-1,3,4-恶二唑(Butyl-PBD)进行了B3LYP/6-31G水平上的分子结构优化、红外光谱、Raman光谱、紫外-可见光谱、分子前线轨道、分子电子密度、Mulliken电荷等理论计算.研究结果表明:理论计算结果与实验数据吻合得较好,对IR、THz、UV-Vis吸收光谱和Raman散射光谱中的特征峰进行了归属,发现Butyl-PBD在0.1～10 THz波谱范围内有五个明显的吸收峰,分别位于2.04THz、3.48THz、5.16THz、6.60THz及7.08THz,Butyl-PBD在紫外光波段有三个吸收波段,分别对应于326.76nm、279.60nm及269.31 nm,其中326.76nm的紫外吸收峰最强.电子密度计算表明,最大电子密度集中在O原子上,N原子的电子密度次之.Mulliken电荷计算表明,负电荷主要集中在O原子和N原子上,所有H原子的Mulliken电荷都为正电荷,C原子的Mulliken电荷则与其具体位置相关.     

OLED绿光掺杂剂DMQA的DFT理论计算研究

采用密度泛函理论(DFT)方法对N,N'-二甲基喹吖啶酮(DMQA)进行了B3LYP/6-31G水平上的分子结构优化、红外光谱、Raman光谱、紫外.可见光谱、分子前线轨道、分子电子密度、Mulliken电荷等理论计算.研究结果表明:理论计算结果与实验数据吻合得较好,对IR、THz、UV-Vis吸收光谱和Raman散射光谱中的特征峰进行了归属,发现DMQA在0.1～10 THz波谱范围内有6个明显的吸收峰,分别位于1.43、2.95、3.81、4.13、6.26以及9.68THz,DMQA在紫外.可见光波段的457.26、386.76及377.37 nm有三个吸收峰,其中457.26 nm的可见光吸收峰最强.电子密度计算表明,最大电子密度集中在O原子和N原子上,O原子的电子密度高于N原子的电子密度.Mulliken电荷计算表明,负电荷主要集中在N原子和O原子上,N原子的Mulliken电荷密度绝对值大于O原子的Mulliken电荷密度绝对值.     

Nonparametric algorithm for local frequency estimation of multidimensional signals

Local frequency (LF) estimation of multidimensional (md) signals is considered. The md-Wigner distribution (WD) is used as the LF estimator. The LF is estimated based on the positions of the WD maxima. A nonparametric algorithm for the LF estimation is developed. It is based on the intersection of confidence intervals rule. This algorithm produces an adaptive window size in the WD which gives almost minimal mean squared error of the estimate. A simplified version of this algorithm is developed, with the starting estimate being produced with the WD of one-dimensional signals. Theory is illustrated in examples.     

Substituent effect of fluorine ligand on spectroscopic properties of Pt(N^C^N)Cl complexes,a theoretical study

Time-Dependent Density Functional Theory (TDDFT) method was used to investigate the substituent effect of fluorine ligand on geometrical structures, electronic properties, electroluminescent properties, absorption and emission spectra of six tridentate cyclometalated Pt(II) complexes. M062X hybrid functional was proved to be suitable for calculating the lowest triplet excited state (T₁) characters in TDDFT calculations. The energies of d–d transitions both in absorption and emission were larger than HOMO–LUMO energy gaps, so d–d transitions did not easily occur. With the introduction of fluorine ligand, the energy levels did not show regularity changes, while the IP (ionization potentials) values and EA (electron affinities) values increased correspondingly. The phosphorescence emissions of the complexes were all assigned as ³ILCT mixed with ³MLCT. In addition, one dimeric form of cyclometalated Pt(II) complexes have also been investigated.     

Significant Improvement of Dye‐Sensitized Solar Cell Performance by Small Structural Modification in π‐Conjugated Donor–Acceptor Dyes

Two donor‐π‐acceptor (D‐π‐A) dyes are synthesized for application in dye‐sensitized solar cells (DSSC). These D‐π‐A sensitizers use triphenylamine as donor, oligothiophene as both donor and π‐bridge, and benzothiadiazole (BTDA)/cyanoacrylic acid as acceptor that can be anchored to the TiO₂ surface. Tuning of the optical and electrochemical properties is observed by the insertion of a phenyl ring between the BTDA and cyanoacrylic acid acceptor units. Density functional theory (DFT) calculations of these sensitizers provide further insight into the molecular geometry and the impact of the additional phenyl group on the photophysical and photovoltaic performance. These dyes are investigated as sensitizers in liquid‐electrolyte‐based dye‐sensitized solar cells. The insertion of an additional phenyl ring shows significant influence on the solar cells' performance leading to an over 6.5 times higher efficiency (η = 8.21%) in DSSCs compared to the sensitizer without phenyl unit (η = 1.24%). Photophysical investigations reveal that the insertion of the phenyl ring blocks the back electron transfer of the charge separated state, thus slowing down recombination processes by over 5 times, while maintaining efficient electron injection from the excited dye into the TiO₂‐photoanode.     

Novel organic dye employing dithiafulvenyl-substituted arylamine hybrid donor unit for dye-sensitized solar cells

In order to increase electron-donating ability of the donor part of the organic dye, two dithiafulvenyl (DTF) units were introduced into a triphenylamine unit to form dithiafulvenyl-substituted triphenylamine hybrid donor for dye-sensitized solar cells (DSSCs) for the first time. Novel donor–acceptor organic dye WD-10 containing this hybrid donor and 2-cyanoacetic acid acceptor has been designed, synthesized and applied in DSSCs. The influence of the substituent unit DTF in the dye on the device performance has been investigated. It was found that the dye with dithiafulvenyl-substituted triphenylamine hybrid donor gave higher photocurrent, open-circuit voltage, and efficiency value. The DSSC based on organic dye WD-10 displayed a short-circuit current (J_sc) of 9.58 mA cm^?2, an open-circuit voltage (V_oc) of 648 mV, and a fill factor (ff) of 0.71, corresponding to an overall conversion efficiency of 4.41%. An increase in η of about 79% was obtained from simple triphenylamine dye L0 to WD-10. The different photovoltaic behaviors of the solar cells based on the organic dyes were further elucidated by the electrochemical impedance spectroscopy. This work identifies that the introduction of DTF unit into the simple triphenylamine dye could significant improve the photovoltaic performance.