超快非均质电子转移的优化控制研究(Ⅱ)

本文用优化控制理论,以分子的基态作为目标态,考虑了在不同条件下,从二萘嵌苯到TiO2超快电子转移的动力学过程.发现在此目标态的作用下,电子经过一个电子激发-回落的过程从分子的基态激发到与半导体导带耦合的第一电子激发态,然后在给定目标态的作用下回落至电子基态,从而实现了较高的目标态产生率.由于二萘嵌苯的电子激发态与半导体导带能级间的强电子转移耦合,这一控制任务较电子激发态为目标态而言,更适合于实验研究.     

飞秒激光作用下异质结的线性吸收谱研究

以二奈嵌苯分子吸附在TiO₂表面所组成的异质结构为例,介绍了在飞秒激光作用下由染料分子和半导体组成的异质结构中从分子基态到半导体导带的超快电子传输过程,在理论上分析了分子内部传输和直接电子传输过程对线性吸收谱的贡献.与分子内部传输过程项相比较分析了电子的超快直接传输在不同的分子及半导体结构下对线性吸收谱的影响. 关键词： 飞秒激光 线性吸收谱 超快电子转移     

飞秒激光控制的分子量子动力学研究：(Ⅰ)三维二能级系统

结合MCDTDH方法和优化控制理论，以吡嗪分子为例，模拟了在给定不同的目标态下具有3个振动模两个电子态的分子系统的量子动力学过程. 以电子激发态作为目标态，优化激光场为一个楔形脉冲，它所激发的电子波函数在两个调制模空间中振荡最后达到平衡位置，并有较高的目标态产生率.发现目标态的选择强烈地影响波函数随时间的演变情况，若目标态在各个模的平衡位置，在优化激光场的作用下，电子波函数被直接激发到其平衡位置；若目标态不在振动模的平衡位形，其电子波函数经过强烈的振荡以达到平衡态. 关键词： 优化控制 MCTDH 方法 分子量子动力学     

芳香族化合物的斯托克斯位移

在分子发光体系中,除具有能量很低的振动能级和容易被热激发电子占据的某些分子外,在大多数情况下,分子是处于基态的零振动能级。当分子吸收了某特定能量被激发到激发态的高振动能级之后,由于不断地与邻近分子碰撞,很快地把多余的振动能转移给邻近分子,最终到达最低的振动能级。因此在电子跃迁中,分子的荧光发射通常是在电子的最低激发态零振动能级与电子基态能级之间进行。     

利用强飞秒激光脉冲串传递相干波包

用一维两态波包动力学模型从理论上研究了碘分子在两个激光脉冲串作用下有泵浦－拉下过程。计算中碘分子的基态和激发态势能面采用莫尔斯势能面,含时薛定谔方程通过分裂算符快速富里叶变换方法求解,基电子态的振动本征函数采采不连续变量方法计算,初步波包选择为电子基态的振动基本征函数,两个势能面之间的耦合采用偶极近似,激光脉冲的形状选择为高斯脉冲。利用上述的含时波包法实时地模拟了碘分子通过中间Ｂ态向基电子Ｘ态的高     

PTCDA分子基态的飞秒激光控制研究

将优化控制理论和多组态含时Hartree（MCTDH）方法相结合,建立了适合于MCTDH方法的计算具有平面结构的PTCDA分子的多自由度振动量子模型,研究了在PTCDA分子激发后从分子激发态回落至分子基态的动力学过程.在理论上分析了约化目标态产生率与激发脉冲、分子的演变时间及优化场的有效能量之间的关系,对分子在各个振动坐标下波函数的振动分布做了分析与比较.研究发现,增加分子的回落演变时间在提高目标态产生率的同时可以使优化激光控制场的强度降低,这为实验上用低能量激光最大程度地实现目标态提供了有效手段. 关键词： PTCDA 多组态含时Hartree方法 飞秒激光控制     

丁胺包裹的CdSe量子点敏化的TiO2纳米晶薄膜电子转移机制

利用超快光谱技术系统研究了在丁胺包裹的CdSe量子点敏化的TiO₂纳米晶薄膜起始时刻界面间电子转移动力学。与之前的报道不同,该实验结果表明:CdSe量子点经过表面修饰后,两相电子注入机制--热电子和冷电子注入得以被证实,即:电子能分别从CdSe量子点导带中高的振动能级和导带底转移到TiO₂的导带。该机制详细描绘了电子在纳米界面间转移的图景。进一步研究发现:热电子注入的电子耦合强度(3.6±0.1 meV)比弛豫后的基态电子注入高两个数量级,基于Marcus理论,伴随着0.083 eV的重组能,冷电子注入的耦合强度值为~50 μeV。     

双分子链中非线性多激子态的动力学研究

在超快激光激发下分子聚集体内有多个激子产生.针对具有链间耦合的双分子链系统,应用密度矩阵理论,在偶极-偶极近似和算符算术平均值近似下通过求解量子主方程计算了不同双链构型下的多激子动力学过程.研究发现在光激发作用下的多激子离域在双链分子系统中,在能量表象下形成激子态能带.激子态能带的宽度和激子占据能级随双分子链构型的不同而不同.对于链间和链内均为H型排列的分子链,激子态能带变宽,激子态优先占据在高阶能级上.在不同能级下的激子具有不同的动力学演变特点.若链间耦合较强,激子态通过链间耦合传递,与分子是否直接受到激发没有直接关系,激发态在两个链内的转移周期与最近邻的链间耦合有直接关系.     

半导体纳米颗粒电子的超快弛豫过程

为了研究在飞秒激光作用下半导体纳米颗粒的超快动力学过程,建立了一个带表面态的三能级结构的载流子弛豫简化模型,得出各能级的电子速率方程.利用数值模拟方法模拟出各能级电子密度和差分吸收率随时间的变化情况,得知由于吸收截面的变化,差分吸收谱会有一个超快的变化过程.并将模拟结果与FanxinWu等人的实验结果相比较,其曲线特征基本一致.说明该模型有一定的合理性.     

半导体纳米颗粒电子的超快弛豫过程

为了研究在飞秒激光作用下半导体纳米颗粒的超快动力学过程,建立了一个带表面态的三能级结构的载流子弛豫简化模型,得出各能级的电子速率方程.利用数值模拟方法模拟出各能级电子密度和差分吸收率随时间的变化情况,得知由于吸收截面的变化,差分吸收谱会有一个超快的变化过程.并将模拟结果与Fanxin Wu等人的实验结果相比较,其曲线特征基本一致.说明该模型有一定的合理性.     

5(6)羧基荧光素敏化TiO2纳米粒子的光致电子转移的荧光特性研究

通过水解TiCl₄制备了锐钛矿结构TiO₂纳米粒子, 并用时间分辨荧光光谱研究了5(6)CFL(5(6)-Carboxyfluorescein, 简称5(6)CFL)染料敏化TiO₂纳米粒子体系的光致电子转移动力学. 5(6)CFL染料敏化TiO₂纳米粒子能形成电荷转移复合物, 这归因于染料分子的激发电子态波函数Ψ(D^*)与电荷分离态波函数Ψ(D⁺ +e^-)之间的耦合作用. 当激发5(6)CFL染料敏化TiO₂纳米粒子体系时, 电子以两种不同方式注入TiO₂纳米粒子导带: 第一, 通过5(6)CFL染料分子的激发态注入; 第二, 从电荷转移复合物(5(6)CFL/TiO₂)直接注入. 时间分辨荧光光谱表明, 在水溶液中纯5(6)CFL染料的荧光以寿命为τ₁=41 ps (74.4%) 和τ₂=3.22 ns (25.6%) 的双e指数衰减, 而5(6)CFL染料敏化TiO₂纳米粒子体系的荧光分别以时间常数为τ₁=44 ps (90.4%), τ₂=478 ps (8.6%) 和τ₃=2.41 ns (1.0%) 的三e指数衰减. 本文的研究工作能够为染料敏化太阳能电池的光致电子转移机理提供有价值的参考.     

DFT and TD-DFT study on structure and properties of organic dye sensitizer TA-St-CA

The geometry, electronic structure, polarizability and hyperpolarizability of organic dye sensitizer TA-St-CA, which contains a π-conjugated oligo-phenylenevinylene unit with an electron donor–acceptor moiety, was studied using density functional theory (DFT), and the electronic absorption spectrum was investigated via time-dependent DFT (TD-DFT) with several hybrid functionals. The calculated geometry indicates that the strong conjugated effects are formed in the dye. The TD-DFT results show that the hybrid functional PBE1PBE and MPW1PW91 are more suitable than B3LYP for calculating electronic absorption spectra. The features of electronic absorption spectra were assigned on account of the qualitative agreement between the experiment and the calculations. The absorption bands in visible and near-UV region are related to photoinduced electron transfer processes, and the diphenylaniline group is major chromophore that contributed to the sensitization, and the interfacial electron transfer are electron injection processes from the excited dyes to the semiconductor conduction band. Compared with the similar dye D5, the good performance of TA-St-CA in dye-sensitized solar cells may be resulted from the higher energy level of the lowest unoccupied molecular orbital and the larger oscillator strengths for the most excited states with intramolecular electron transfer character.     

Geometries, electronic structures and vibrational spectral studies of 4-aminophthalonitrile using quantum chemical calculations for dye sensitized solar cells

The geometries, electronic structures, polarizabilities, and hyperpolarizabilities of organic dye sensitizer 4-Aminophthalonitrile were studied based on Hartee-Fock (HF) and Density Functional Theory (DFT) using the hybrid functional B3LYP. Ultraviolet-visible (UV-Vis) spectrum was investigated by Time Dependent DFT (TD-DFT). Features of the electronic absorption spectrum in the visible and near-UV regions were assigned based on TD-DFT calculations. The absorption bands have been assigned to n → π* transitions. Calculated results suggest that the three excited states with the lowest excited energies in 4-Aminophthalonitrile is due to photoinduced electron transfer processes. The interfacial electron transfer between semiconductor TiO₂ electrode and dye sensitizer is due to an electron injection process from excited dye to the semiconductor’s conduction band. The role of cyanide and amine group in 4-Aminophthalonitrile geometries, electronic structures, and vibrational spectra were compared with experimental values and in view of these results, it was concluded that 4-Aminophthalonitrile used in Dye Sensitized Solar Cells (DSSC) gives a good conversion efficiency.     

不对称菁染料敏化纳米TiO2的光生电流过程

用光电化学方法研究了不对称菁类染料敏化TiO2 纳米结构电极的光电转换过程 .结果表明 ,该染料的电子激发态能级位置与TiO2 纳米粒子导带边位置匹配较好 ,光激发染料后 ,其激发态电子可以注入到TiO2 纳米多孔膜的导带 ,从而使TiO2 纳米结构电极的吸收光谱和光电流谱红移至可见光区 ,其IPCE(Incidentphoton to electronconversionefficiency)值最高可达 84.3 % .并进一步结合现场紫外 可见吸收光谱研究了外加电势对激发态染料往TiO2 纳米多孔膜注入电子过程的影响     

Coherent longitudinal-optical ground-state phonon in CdSe quantum dots triggered by ultrafast charge migration

We observe the CdSe longitudinal-optical ground-state phonon in the electron transfer system composed of CdSe quantum dots and methylviologen directly by femtosecond absorption spectroscopy. A significant phase shift indicates that the coherent oscillations are triggered by an ultrafast charge migration, which is the consequence of an electron transfer from the photoexcited quantum dot to the molecular acceptor methylviologen. In contrast, the observed coherent phonons in isolated quantum dots stem from the frequency modulation of the quantum dot excited-state spectrum. From the probe wavelength dependence of the longitudinal-optical phonons in the electronic ground state and excited state it is possible to determine a biexciton binding energy of 35?meV.     

Photoinduced Intramolecular Electron Transfer and Electronic Coupling Interactions in π- Expanded Imidazole Derivatives

An intramolecular excited charge transfer (CT) analysis of imidazole derivatives has been made. The determined electronic transition dipole moments has been used to estimate the electronic coupling interactions between the excited charge transfer singlet state (¹CT) and the ground state (S₀) or the locally excited state (¹LE). The properties of excited ¹CT state imidazole derivatives have been exploited by the significant contribution of the electronic coupling interactions. The excited state intramolecular proton transfer (ESIPT) analysis has also been discussed.     

Electron injection dynamics in dye-sensitized semiconductor nanocrystalline films

We have summarized recent ultrafast spectroscopic studies on phenomena associated with dye-sensitization of semiconductor metal oxide nanoparticles, especially TiO₂ nanocrystalline film from a surface science perspective with a strong relation to mechanism of electron injection in dye-sensitized solar cells, which are attracting much interest from both viewpoints of pure science and applied science.A lot of chemical and physical processes are involved in this solar cell, such as light harvesting by molecules and nanostructures, interfacial electron transfer, charge migration in solid and electrolyte, degradation of the materials, and so on. Among them, the very primary process initiated by photoabsorption by sensitizing dye molecules; that is, electron injection from excited adsorbates into the conduction band of semiconductor metal oxides is significantly important, because this process must be 100% efficient with a minimum driving force for high current and voltage generation.We have first focused on details of experimental methods used in this research area, and then in the following Sections, have organized this review by concentrating on each parameter that influences dynamics of electron injection in dye-sensitized semiconductors. Finally we have emphasized it is important to measure actual DSSCs for the precise comparison between electron injection dynamics and device performance.     

Bonded exciplex formation from stacked thymine and adenine: semiclassical simulations

The nonradiative decay of a π-stacked adenine and thymine, following excitation of thymine by an ultrafast laser pulse, was studied by semiclassical dynamics simulations. The simulation found that a bonded exciplex is formed after excitation due to strong interaction between the stacked bases. The strong interaction significantly lowers the energy gap between the LUMO and HOMO and consequently facilitates the deactivation of the electronically excited molecule. It also restricts the deformation vibration of the excited thymine molecule, which slows down the coupling between the HOMO and LUMO energy levels and delays the deactivation of the excited adenine molecule to the electronic ground state.