4氢-吡喃-4-硫酮1(n-π*),1Ag-(π→π*)和1Bu+(π→π*)等的激发态特征

理论上4氢-吡喃-4-硫酮的激发态特征用量子化学方法以及二维实空间分析法和三维立体实空间分析法加以研究.理论上的结果揭示1(n→π*)和1Ag-(π→π*)激发态是分子内电荷转移(ICT)激发态,而1Bu (π→π*)激发态是离域激发态.它们的跃迁偶极矩的强度和方向用三维密度跃迁(TD)加以解释,用三维电荷密度差(CDD)观察分子间电荷转移(ICT)的激发态特征或局部激发态特征.用二维实空间分析法研究电子.空穴相关性,离域化和激子的尺寸.     

4氢-吡喃-4-硫酮~1(n→π*),~1A_g~-(π→π*)和~1B_u~+(π→π*)等的激发态特征(英文)

理论上4氢-吡喃-4-硫酮的激发态特征用量子化学方法以及二维实空间分析法和三维立体实空间分析法加以研究.理论上的结果揭示^1（n→π^＊）和^1Ag^-（π→π^＊）激发态是分子内电荷转移（ICT）激发态,而^1Bu^＋（π→π^＊）激发态是离域激发态.它们的跃迁偶极矩的强度和方向用三维密度跃迁（TD）加以解释,用三维电荷密度差（CDD）观察分子间电荷转移（ICT）的激发态特征或局部激发态特征.用二维实空间分析法研究电子-空穴相关性,离域化和激子的尺寸.     

ZnSe在外电场下的基态性质和激发特性研究

以LANL2DZ为基组, 采用Hartree-Fock(HF)方法研究了不同外电场(-0.025–0.040 a.u.)对ZnSe分子的基态几何结构、电荷分布、能量、电偶极矩、最高占据轨道(HOMO)能级、最低空轨道(LUMO)能级、能隙、红外光谱特性的影响; 继而采用含时的TD-HF方法研究了ZnSe分子在外电场下前9 个激发态的吸收谱、激发能、振子强度等激发特性. 研究结果表明: 当电场从-0.025 a.u.变化到0.04 a.u. 时, 键长先减小后增加; 分子偶极矩先由正减小到0, 然后又反向增加; 体系总能量一直减小; 谐振频率先增加后减小, 红外光谱强度先减小后又增加. ZnSe分子的LUMO能级一直增加, HOMO能级先增加后又减小, 变化趋势较小, 而能隙一直增大. 外电场对ZnSe分子的激发特性影响较大, 当电场从-0.025 a.u.变化到0.04 a.u.时, 激发能增加, 相应的激发波长减小; 对应的振子强度也受到很大影响, 原来振子强度最强的激发态变得很弱, 而原来振子强度很弱的激发态变得最强. 因此, 可以通过改变电场来控制ZnSe的激发特性.     

Photoinduced Intramolecular Charge Transfer in Donor-acceptor Dyad and Donor-bridge-acceptor Triad

在fullerene-PBTDP-TPA三体体系中的光诱导的分子内电荷转移的实验基础上,分别利用密度泛函理论和含时密度泛函理论以及结合二维、三维实空分析方法对fullerene、PBTDP-TPA二体以及fullerene-PBTDP-TPA三体的基态和激发态的性质进行了理论研究．二维定点表象揭示了激发情况下电子和空穴的相干情况．三维跃迁矩阵展示了跃迁偶极矩的方向和强度,而且三维电荷差密度给出了光诱导的分子内电荷转移的方向和结果．同时,用二维和三维表象的方法对fullerene-PBTDP-TPA三体中光诱导的分子内电荷转移过程进行了验证,揭示了在给予者-桥-接收者三体分子体系中分子内激发时电荷转移的机制．除此之外,还发现直接从给予者到接收者超交换的分子内电荷转移极大地促进了给予者-桥-接收者三体分子体系内的电荷转移．     

外电场作用下乙酸乙烯酯的分子结构和激发态

采用密度泛函B3LYP方法在6-31G(d)基组水平上,计算了乙酸乙烯酯分子在不同外电场(0.000 a.u.~0.030 a.u.)作用下的基态几何结构、电偶极距、电荷分布及分子总能量,然后利用杂化CIS-DFT方法在相同基组下研究了外电场对乙酸乙烯酯分子前8个激发态的激发能、波长和振子强度的影响.结果表明,分子的几何结构、电荷分布与外电场的大小呈现强烈的依赖关系.随着外电场的不断增加,分子的总能量逐渐减小,偶极距逐渐增大,激发能随电场的增加总体上呈减小的趋势,表明在外电场作用下,乙酸乙烯酯分子易于激发,激发态波长随电场的增加总体上呈增大的趋势,且电子跃迁光谱都集中在紫外区.     

Fully conjugated push–pull dendrons with high dipole moments in excited state; synthesis and theoretical rationalization

Novel fully conjugated push–pull dendrons were synthesized by a divergent approach to evaluate the performance of non‐conventional architectures like dendritic one in charge separation processes associated with photovoltaic events. The dipole moments in excited state were estimated by the solvatochromic method, to be related to the charge separation efficiency. A 1:2 ratio of donor–acceptor groups (methoxy and nitro groups respectively) promotes the largest dipole moment in both ground and excited state (up to 17 D), due to the efficient electron density transfer over the entire molecule, through the π‐electron system. The synthesized dendrons induce charge transfer on excitation as follows from UV–vis absorption–emission analysis and theoretical calculations. Copyright © 2015 John Wiley & Sons, Ltd.     

含芴酮的低聚物的激发态特征研究

采用量子化学计算方法和跃迁密度及电荷差分密度分析方法对含芴酮的低聚物激发态性质进行理论研究。计算得到的跃迁能和振子强度与实验数据一致。跃迁密度分析显示跃迁偶极矩的大小和方向,电荷差分密度分析揭示了分子间电荷转移的方向和结果。研究表明含芴酮的低聚物在光诱导下产生的第一激发态为分子内电荷转移激发态,而第五激发态为局域激发态。跃迁密度矩阵分析和电荷差分密度的理论分析结果易于理解含芴酮低聚物的激发态特性。     

含芴酮的低聚物的激发态特征研究

采用量子化学计算方法和跃迁密度及电荷差分密度分析方法对含芴酮的低聚物激发态性质进行理论研究。计算得到的跃迁能和振子强度与实验数据一致。跃迁密度分析显示跃迁偶极矩的大小和方向,电荷差分密度分析揭示了分子间电荷转移的方向和结果。研究表明含芴酮的低聚物在光诱导下产生的第一激发态为分子内电荷转移激发态,而第五激发态为局域激发态。跃迁密度矩阵分析和电荷差分密度的理论分析结果易于理解含芴酮低聚物的激发态特性。     

(ZnSe)_(12)在外电场下的基态性质和激发特性研究

以SBKJC为基组,采用密度泛函PBE0方法研究了不同外电场(0-0.030 a.u.)对(ZnSe)_(12)的基态几何结构、电荷分布、能量、电偶极矩、能隙、最小振动频率的影响;继而采用含时的TD-PBE0方法研究了(ZnSe)_(12)在外电场下的激发特性,并模拟了紫外-可见光谱.研究结果表明:外电场的加入导致分子对称性降低,当电场从0 a.u.变化到0.030 a.u.时,偶极矩逐渐增加,体系总能量、最小谐振频率和能隙一直减小.外电场对(ZnSe)_(12)的激发特性影响较大,随着电场的增加,紫外-可见光谱发生红移,同时对振子强度有很大影响,原来振子强度不为零的激发态变弱或成为禁阻跃迁,而原来振子强度很弱或禁阻的激发态变得很强.可以通过改变外电场来改变(ZnSe)_(12)的基态性质,以及控制(ZnSe)_(12)的吸收和发光特性.     

石墨烯量子点的磁性及激发态性质

利用密度泛函理论在B3LYP/6-31G(d)基组水平上研究了具有zigzag边界的石墨烯量子点,结果表明不同大小的石墨烯量子点的基态都是具有磁性的自旋三重态.其磁性一方面来源于zigzag边界上占有凸出位置的碳原子,另一方面来源于带有孤对电子的碳原子.从整体上看,除6b结构外,其他结构的能隙随着苯环数量的增加逐渐减小,而附加电荷却使体系能隙明显减小.用含时密度泛函理论(TD-DFT)对能隙为3.83 eV的由六个苯环排列成的三角形结构进行了激发态的计算,发现第十七激发态强度最大,能量为3.93 eV,对 关键词： 石墨烯量子点 磁性 能隙 激发态     

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.     

Excited State Properties of Fluorine-Substituted Hexabenzocoronene: A Quantum-Chemical Characterization

The first fluorine-substituted hexabenzocoronene has been synthesized and its electronic structure and optical properties have been reported [Q. Zhang, et al., Org. Lett.7 (2005) 5019]. In this letter, the electronic structure and excited state properties of the fluorine-substituted hexabenzocoronene are studied with quantum chemistry method as well as the transition and the charge difference densities. The transition densities show the orientations and strength of the dipole moments and the charge difference densities reveal the orientation and results of the intramolecular charge transfer. The calculated transition energies and oscillator strengths are consistent with the experimental data, and the theoretical results of transition and charge difference densities are valuable to understanding the excited state properties of the fluorine-substituted hexabenzocoronene.     

Molecule opacity study on low-lying states of CS

CS molecule, which plays a key role in atmospheric and astrophysical circumstances, has drawn great attention for long time. Owing to its large state density, the detailed information of the electronic structure of CS is still lacking. In this work, the high-level MRCI+Q method is used to compute the potential energy curves, dipole moments and transition dipole moments of singlet and triplet states correlated with the lowest dissociation limit of CS, based on which high accurate vibration—rotation levels and spectroscopic constants of bound states are evaluated. The opacity of CS relevant to atmospheric circumstance is computed at a pressure of 100 atms for different temperatures. With the increase of temperature, band systems from different transitions mingle with each other, and band boundaries become blurred, which are originated from the increased population on vibrational excited states and electronic excited states at high temperature.     

Excited State Properties of Fluorine-Substituted Hexabenzocoronene： A Quantum-Chemical Characterization

The first fluorine-substituted hexabenzocoronene has been synthesized and its electronic structure and optical properties have been reported [Q. Zhang, et al., Org. Lett. 7 （2005） 5019]. In this letter, the electronic structure and excited state properties of the fluorine-substituted hexabenzocoronene are studied with quantum chemistry method as well as the transition and the charge difference densities. The transition densities show the orientations and strength of the dipole moments and the charge difference densities reveal the orientation and results of the intramolecular charge transfer. The calculated transition energies and oscillator strengths are consistent with the experimental data, and the theoretical results of transition and charge difference densities are valuable to understanding the excited state properties of the fluorine-substituted hexabenzocoronene.     

Solvent Effects on the Spectroscopic Properties of Styrylquinolinium Dyes Series

The study on the relationship between the structure and spectroscopic properties of styrylquinolinium dyes were carried out by measuring the electronic visible absorption, steady-state and time-resolved fluorescence spectra of quinoline based hemicyanine dyes. The influence of the solvent on absorption and emission spectra and the solvatochromic properties, observed for both ground and first excited states, for all the dyes were applied for the evaluation of their excited state dipole moments. The ground state dipole moments of dyes under the study were established by applying ab initio calculations. The measured, using solvatochromic methods, excited state dipole moments of tested hemicyanines are in the range from 5.38 to 18.90 D and the change in the dipole moments caused by excitation were found to differ from 1.88 to 6.64 D. It was observed that for all tested dyes the dipole moments of the excited states were higher than those of a ground states. The fluorescence lifetime measurements with picosecond resolution was performed for entire series of hemicyanine dyes possessing different dialkylamino groups attached to the phenyl ring. The average lifetimes of the dye fluorescence, determined from the measured data by multi-order exponential decay curve fitting, were in the range from about 120 to 1200 ps at the fluorescence peak wavelength. The fluorescence lifetime measurements were performed for dyes in ethyl acetate solutions. The time-resolved fluorescence spectra measurements allowed to propose the mechanism of the dyes excited states deactivation.     

外场下丙烯酸甲酯的激发特性研究

采用密度泛函B3LYP方法在6-311+ +G* *基组上优化了不同外电场作用下丙烯酸甲酯分子的基态几何结构、电偶极矩和分子的总能量,并且分析了分子的HOMO-3到LUMO+3轨道的能量变化,然后利用杂化CIS-DFT方法(CIS-B3LYP)在相同基组下探讨了无电场时丙烯酸甲酯分子前9个激发态的激发能、波长和振子强度和外电场对丙烯酸甲酯分子激发态的影响规律.结果表明,分子的几何构型与外电场大小有着较强的依赖关系.随着外电场的增大,分子总能量先增大后减小,电偶极矩μ先减小后增大,激发能随电场 关键词： 丙烯酸甲酯 外电场 振子强度 激发能     

二氢化钚分子激发态结构的外场效应

采用密度泛函(DFT)方法B3LYP/Gen，在Pu为SDD基组、H为6-311++G^**基组水平上优化得到了分子轴方向不同电偶极场(-0.005—0.005a.u.)作用下，二氢化钚的基态电子状态、几何结构、电偶极矩和分子总能量.在优化构型下用同样的基组采用含时密度泛函(TDDFT)方法(TD-B3LYP)研究了同样外电场条件下对二氢化钚的激发能和振子强度的影响.计算结果表明，分子几何构型与电场大小和方向呈现较强的依赖，电场强度增加基态偶极矩随电场强度线性增加，H-Pu-H的角度线性减小，分子总能量线性减小；激发能随电场强度增加而减小，且对电场方向的依赖呈现近似对称性，满足Grozema关系.电场对振子强度的影响比较复杂，但仍满足跃迁选择定则. 关键词： 二氢化钚 激发态 电偶极场 TD-DFT     

Theoretical investigation of the ground and excited state of silylated coumarin

We present ground and excited state properties of silylated coumarin dyes. We have calculated the energies and dipole moments of ground and excited states of silylated coumarins and some coumarin derivatives. Using CIS we find a good agreement with experimental S₀→S₁ excitation energies. Silylation of dye molecules had minor effect on the transition energies. On the basis of theoretical results, we conclude that silylated dye will have improved long-term photostability compared to its unsilylated counterpart due to its covalent bonding with the host matrix.