DFT/TDDFT investigation on the photophysical properties of a series of phosphorescent cyclometalated complexes based on the benchmark complex FIrpic

The photophysical properties of four Ir(III) complexes have been investigated by means of the density functional theory/time-dependent density functional theory (DFT/TDDFT). The effect of the electron-withdrawing and electron-donating substituents on charge injection, transport, absorption and phosphorescent properties has been studied. The theoretical calculation shows that the lowest-lying singlet absorptions for complexes 1–4 are located at 387, 385, 418 and 386 nm, respectively. For 1–4, the phosphorescence at 465, 485, 494 and 478 nm is mainly attributed to the LUMO → HOMO and LUMO → HOMO-1 transition configurations characteristics. In addition, ionisation potential (IP), electron affinities (EAs) and reorganisation energy have been investigated to evaluate the charge transfer and balance properties between hole and electron. The balance of the reorganisation energies for complex 3 is better than others. The difference between hole transport and electron transport for complex 3 is the smallest among these complexes, which is beneficial to achieve the hole and electron transfer balance in emitting layer.     

超强飞秒激光脉冲作用下氢分子的高次谐波行为——基于含时密度泛函理论的模拟

在含时密度泛函理论框架下,采用经典和量子相结合的模型,模拟了氢分子在超强飞秒激光脉冲作用下的高次谐波行为. 结果表明氢分子的高次谐波谱具有“下降—平台—截止”的结构和偶次谐波被禁闭仅出现奇次谐波的选择性特征;不同的激光偏振方向会导致高次谐波的截止频率和谱线强度的变化. 关键词：TDDFT超强飞秒激光高次谐波2分子')\" href=\"#\">H₂分子     

两种结构的C4分子在激光场中的响应

运用含时密度泛函理论和分子动力学相结合的方法,研究线形和环形C4分子的光吸收谱及在强激光场中的电子和离子响应.研究表明,在相同的激光参数下,线形C4分子主要是电子获得能量,而环形C4分子主要是离子获得能量;线形C4分子的电离增强,x方向的激光场仅激发起线形C4分子的Dx的偶极振动,但是能激发起环形C4分子Dx的偶极振动及Dy的非偶极振动.     

Theoretical study on the electronic structures and phosphorescent properties of four Ir(III) complexes with different substituents on the ancillary ligand

The geometry structures, electronic structures, absorption and phosphorescent properties of four Ir(III) complexes {[(F₂-ppy)₂Ir(pta-X)], where F₂-ppy = (2,4-difluoro)phenylpyridine; pta = pyridine-1,2,4-triazole; X = –CF₃; –H; –CH₃; –N(CH₃)₂}, are investigated using the density functional method. The results reveal that the electron-accepting group –CF₃ has no obvious effect on absorption and emission properties, while the substitutive group –N(CH₃)₂ with strong electron-donating ability has obvious effect on the emission properties. The mobility of hole and electron were studied computationally based on the Marcus–Hush theory. Calculations of ionisation potential and electron affinity were used to evaluate the injection abilities of holes and electrons into these complexes. We hope that this theoretical work can provide a suitable guide to the future design and synthesis of novel phosphorescent materials for use in the organic light-emitting diodes.     

对氨基二苯甲酮光吸收和光反应活性的含时密度泛函研究

利用含时密度泛函理论研究了对氨基二苯甲酮(p-ABP )的气液相吸收光谱性质．结果表明,p-ABP单重态的性质随着溶剂极性的变化发生明显的改变．在极性溶剂乙腈、甲醇、乙醇、二甲亚砜和二甲基甲酰胺中,S1态是产生于π→π*跃迁的电荷转移态;在非极性溶剂环己烷和苯中,S1态是产生于n→π*跃迁的局域激发态．对于p-ABP三重态的计算结果表明,无论是极性溶剂中还是非极性溶剂中T1态都具有π→π*构型．不同溶剂中激发态构型和跃迁能的变化情况表明,对应于n→π*跃迁的吸收光谱随着溶剂极性的增加出现明显的蓝移,对应于π→π*跃迁的吸收光谱则随溶剂极性的增加出现明显红移．通过对计算结果进行分析,讨论了对氨基二苯甲酮三重态量子产率在不同溶剂中的变化情况和它在氢提取反应中表现出低光还原反应活性原因．     

新型双色有机电致磷光器件

所研究的有机电致磷光发光器件(OLED)选用了一种新型金属铱的化合物Ir(C6)₂(acac),这种金属化合物由配位体香豆素C6和乙酰丙酮(acac)与金属铱化合形成。Ir(C6)₂(acac)可同时作为电子传输材料和发光掺杂剂。比较香豆素C6和Ir(C6)₂(acac)固体材料的光致发光谱,可见Ir(C6)₂(acac)明显抑制了有机电致发光材料分子与分子之间的发光猝灭效应。采用ITO/TPD(N,N′-diphenyl-N,N′-bis(3-methyl-phenyl)-1,1′biphenyl-4,4′diamine)/Ir(C6)₂(acac)/BAlq(bis(2-methyl-8-quinolinolato-N₁,O₈)-(1,1′-biphenyl-4-olato)aluminum)/Alq₃aluminum/Liq(8-hydroxyquinolinelithium)/Al结构,可得到CIE(Commission Interationaled′Eclairage)值为x=0.43;y=0.40的橙红色发光器件,最高亮度可达3390cd/m₂,最大电流效率为1.3cd/A。采用同样的器件结构以Ir(C6)₂(acac)掺杂Alq₃主体得到绿色发光器件,发光色的CIE坐标值为x=0.29;y=0.58,最高亮度可达8832cd/m₂,最大电流效率为5.6cd/A。器件的发光机理研究表明Ir(C6)₂(acac)的非掺杂器件发光以Ir(C6)₂(acac)的三线态磷光为主,器件发光为橙色;在Alq₃中的单掺杂器件以Alq₃和Ir(C6)₂(acac)的荧光为主,同时有小比例Ir(C6)₂(acac)的三线态磷光成分存在,器件总体发光为绿色。     

High-performance organic red-light-emitting device based on DCJTB and a new host material

An efficient red-light-emitting device using a new host material (DPF) and a red dopant (DCJTB) with a configuration of ITO/NPB (50 nm)/DCJTB:DPF (2%, 10 nm)/TPBI (30 nm)/LiF (0.5 nm)/Mg:Ag has been fabricated and investigated. The red OLED yields a brightness of 9270 cd/m² at 10 V, a maximum current efficiency of 4.2 cd/A and a maximum power efficiency of 3.9 lm/W. Using DPF as host material, the performance is much better than that of a prototypical Alq₃-based device, which has a maximum efficiency of 1.9 cd/A and 0.6 lm/W. The performance is even comparable with red OLEDs using an assist dopant or a cohost emitter system. Results of this work indicate that DPF is a promising host material for red OLEDs with high efficiency and simple device structure.     

Optical properties of clusters and molecules from real-time time-dependent density functional theory using a self-consistent field

We present a detailed study of optical absorption spectra of finite-size structures, using a method based on time-dependent density-functional theory (TDDFT), which involves a self-consistent field for the propagation of the Kohn–Sham wavefunctions in real-time. Although our approach does not provide a straightforward assignment of absorption features to corresponding transitions between Kohn–Sham orbitals, as is the case in frequency-domain TDDFT methods, it allows the use of larger timesteps while conserving total energy and maintaining stable dipole moment oscillations. These features enable us to study larger systems more efficiently. We demonstrate the efficiency of our method by applying it to a hydrogen-terminated silicon cluster consisting of 364 atoms, with and without P impurities. For cases where direct comparison to experiment can be made, we reproduce the absorption features of fifteen small molecules [N₂, O₂, O₃, NO₂, N₂O, NH₃, H₂O, H₂CO, H₂CO₃, CO₂, CH₄, C₂H₂, C₂H₄, C₂H₆, C₆H₆] and find generally good agreement with experimental measurements. Our results are useful for the detection and the determination of orientation of these molecules.     

15eV的质子与羟基碰撞的动力学

采用含时密度泛函理论和分子动力学非绝热自洽耦合的方法,全微观研究沿垂直羟基分子轴向入射初动能为15 eV的质子与羟基碰撞过程的电子-离子关联动力学.计算质子和羟基动能、碰撞后羟基电子和离子的运动状态及系统电子密度的实时分布.结果表明:质子与羟基碰撞后俘获羟基的一部分电子被反弹并损失26.7%的初始动能而羟基动能增加.碰撞后丢失1%电子的羟基在保持碰撞前收缩振动的同时向计算边界平动并以93%的中性和7%的+1价的几率存在.     

有机电致发光中的电致激基复合物

获得了一种基于电致激基复合物的高效率白光有机电致发光器件,采用p-i-n结构,有效地降低了器件的工作电压。器件的最大亮度为9050cd/m²,最大功率效率为2.63lm/W。随着电压的增加,器件的CIE色坐标一直处于白光区域。     

共轭聚合物中掺杂可溶性石墨烯对于OLED和OPV性能的影响

本文重点研究了不同浓度可溶性石墨烯(SPFGO)对于聚[2-甲氧基-5-(2-乙基己氧基)]对苯乙炔(MEH-PPV)/SPFGO复合薄膜的光致发光(PL)、 有机电致发光(OLED)和有机光伏(OPV)性能的影响. 研究发现, 在MEH-PPV中掺杂SPFGO之后, MEH-PPV/SPFGO复合薄膜的光致发光发生了非常强烈的猝灭, 意味着MEH-PPV和SPFGO之间发生了非常强烈的载流子传输. 当SPFGO的浓度较低的时候, 能够提高OLED的性能, 当SPFGO的浓度为0.2%时, OLED的性能达到最佳, 而此时的OPV性能基本没有改变. 当掺杂较高浓度的SPFGO 之后, OPV的性能有了明显的提升, 当浓度为15%时, OPV达到了最佳的性能, 而此时的OLED发生了非常强烈的猝灭. 通过实验数据可以看出, 当SPFGO较低浓度的时候, 起到增强载流子注入的作用, 提升OLED亮度的同时降低了开路电压. 而当SPFGO达到较高浓度时, SPFGO作为电子受体, 可以起到改善MEH-PPV/SPFGO 界面激子分裂和提高OPV性能的作用. 因此, 通过调节SPFGO浓度可以起到独立调控OLED性能和OPV性能的作用.关键词：SPFGOOLEDOPV     

TD-DFT investigation of electronic structures,photophysical properties and the theoretical design of OLEDs based on phosphorescent Ir(III) complexes bearing the non-π electron-conjugated carbene ligand

In the search for efficient phosphorescent materials, a rational design is presented for the iridium complex material (dfbmb)Ir(fptz)₂ (2) (dfbmb?=?1-(2,4-difluorobenzyl)-3-methylbenzimidazolium), which involves the use of two 2-pyridyl triazolate (fptz) chromophores and a non-π electron-conjugated high-field ligand dfbmb assembled by a saturated σ-bond methylene group, and a comparison with the benchmark (dfbmb)₂Ir(fptz) (1). In this work the electronic structures, absorption and phosphorescence spectra were investigated using the TD-DFT method. In order to obtain the mechanism of high phosphorescence yield in (1) and estimate the radiative rate constant k _r for (2), the radiative rate constant k _r, the spin-orbital coupling (SOC) matrix element, ΔE(S???T), and the square of the SOC matrix element (?ψ_S1|H_SO|ψ_T1?²) for (1) and (2) were measured. It is concluded that the switch of the cyclometalated ligand from the main chelate to the ancillary chelate seems to enhance the splitting of ΔE(S???T) in the current system. Finally, using the information gained, a PhOLED utilizing (1) and (2) was designed.     

Molecular dynamics study of the formation of small crystallites of Lennard-Jones particles in slit-like pores with (100) fcc walls

Canonical ensemble molecular dynamics is used to investigate the formation of small crystallites in slit-like pores with crystalline walls of (100) fcc symmetry. We study the influence of the pore width and the energetic parameters of the fluid particle-pore wall potential on the structure of the frozen droplets. We analyse the density profiles, in-plane radial distribution functions, in-plane diffusion coefficients, the distributions of Voronoi polygons, as well as the snapshots of consecutive configurations.