Localized self-trapping in the two-dimensional discrete molecular lattice with the interaction between Frenkel excitons and phonons

We investigate the interactions of lattice phonons with Frenkel exciton, which has a small radius in a twodimensional discrete molecular lattice, by the virtue of the quasi-discreteness approximation and the method of multiplescale, and obtain that the self-trapping can also appear in the two-dimensional discrete molecular lattice with harmonic and nonlinear potential. The excitons＇ effect on the molecular lattice does not distort it but only causes it to localize which enables it to react again through phonon coupling to trap the energy and prevent its dispersion.

Evaluating First-Order Molecular Properties of Delocalized Ionic or Excited States in Molecular Aggregates by Renormalized Excitonic Method

In the past few years,the renormalized excitonic model(REM)approach was developed as an efficient low-scaling ab initio excited state method,which assumes the low-lying excited states of the whole system are a linear combination of various single monomer excitations and utilizes the effective Hamiltonian theory to derive their couplings.In this work,we further extend the REM calculations for the evaluations of first-order molecular properties(e.g.charge population and transition dipole moment)of delocalized ionic or excited states in molecular aggregates,through generalizing the effective Hamiltonian theory to effective operator representation.Results from the test calculations for four different kinds of one dimensional(1D)molecular aggregates(ammonia,formaldehyde,ethylene and pyrrole)indicate that our new scheme can efficiently describe not only the energies but also wavefunction properties of the low-lying delocalized electronic states in large systems.

Exciton Energy Transfer in Hybrid Organics—Semiconductor Nanostructure

We consider a hybrid heterostructure containing an inorganic quantum well in close proximity with organic material as overlayer. The resonant optical pumping of Frenkel exciton can lead to an efficient indirect pumping of Wannier excitons. As organic material in such a hybrid structure, we consider crystalline tetracene. In tetracene, the singlet exciton energy is close to twice the one of triplet exciton state and singlet exciton fission into two triplets can be efficient. This process in tetracene is thermally activated and we investigate here how the temperature-dependent exciton energy transfer affects the functional properties of hybrid organic-inorganic nanostructures. We have obtained the exact analytical solution of diffusion equation for organics at different temperatures defining different diffusion lengths of excitons. The effectiveness of energy transfer in hybrid with tetracene was calculated by definite method for two selected temperatures that open possibility to operate in full region of temperatures. Temperature dependence of energy transfer opens a new possibility to turn on and off the indirect pumping due to energy transfer from the organic subsystem to the inorganic subsystem.

叶黄素聚集体吸收光谱的实验分析与理论模拟

分子聚集体表现出单分子所不具备的特有功能,利用吸收光谱对聚集体分子结构特性的研究是理解其电子和能量转移功能的基础。实验中利用紫外-可见分光光度计,检测了叶黄素在乙醇溶液中的单体吸收谱和在1∶1乙醇水溶液中的聚集体吸收谱。并通过对叶黄素单体吸收谱的高斯分解,获得了激发态的振动能级结构参数。理论上采用时间相关函数描述的吸收谱线和Frenkel激子模型,通过模拟单分子吸收光谱,获得了叶黄素分子的激发能、特征模振动频率、Huang-Phys因子等参数。再利用这些参数进行了聚集体分子光谱的模拟,分析了叶黄素聚集体的分子结构影响光谱变化的原因。结果表明,(1)分子间的相互作用是决定吸收光谱峰位移动的主要原因,实验中叶黄素H-聚集体的吸收光谱较单体蓝移了77nm,模拟显示相互作用在2 000cm-1附近;(2)聚集体分子个数越多,聚集协作效应越大,吸收光谱半高宽变小,同时吸收峰进一步蓝移;(3)环境的无序度对吸收光谱的半高宽也存在较大的影响,无序度越大,吸收光谱半高宽越大。实验结果为进一步研究聚集体在生物系统和材料系统中的功能提供了理论依据。

分子聚集体的光谱模拟

采用Frenkel激子理论研究了一维线性和二维人字形分子聚集体的吸收和发射光谱.通过引入激子离域长度的概念,将聚集体与单分子的光谱线形函数联系起来.计算的光谱结果表明,聚集体的光谱与分子在聚集体中的排列紧密相关.分析了一维J聚集光谱发生红移以及二维人字形分子聚集体吸收光谱形成J和H激子谱带的内在原因.模拟得到的聚集体的吸收和发射光谱与实验结果一致.

混合分子聚集体有机纳米材料中相干与非相干皮秒脉冲累积光子回波

用双调制（斩波器和驻波调制器）和外差检测累积光子回波技术，研究了ＰＩＣ－Ｉ和ａｚａＰＩＣ－Ｉ混合分子集体有机纳米材料中一维Ｆｒｅｎｋｅｌ激子的位相弛豫过程．观测到激子失相时间Ｔ２随ａｚａＰＩＣ－Ｉ克分子数的增大从６０ｐｓ变为２２４ｐｓ．这与在含能量陷阱的分子聚集体中激子失相时间Ｔ２随陷阱的增加而变短的现象刚好相反．并且对在脉宽为４ｐｓ和相于时间为１ｐｓ的相干脉冲和非相干脉冲的不同激发条件下的实验结果进行了分析和讨论．

BaF_2中V_k心的ESR谱分析

电子自旋共振(ESR)实验间接表明,γ射线辐照能在室温下在BaF2微晶中产生Frenkel激子这样的元激发,此元激发受热在150℃以下消失。γ射线辐照使BaF2微晶中F-离子上的2P电子跃迁到外层轨道,并与2P轨道的空穴形成紧束缚的电子-空穴对——Frenkel激子。激子中的电子受热脱离F原子,这种晶格上的F0是ESR可探测的顺磁色心点缺陷——Vk心。受γ射线辐照的BaF2微晶中含有Frenkel激子,受热时Frenkel激子湮灭。Vk心增多的现象。

Gamma ray irradiation induced point defects in BaF_2

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Transient photovoltage and photoluminescence study of exciton dissociation at indium tin oxide/pentacene interface

The exciton dissociation at ITO/pentacene interface is studied by means of transient photovoltage measurement.Opposite to ITO/NPB,ITO/CuPc or ITO/C60 interface where polarity change of transient photovoltage is observed,no interfacial dissociation is found at room temperature,which indicates a lack of Frenkel excitons in pentacene.Temperature-dependent photoluminescence (PL) is investigated.More like the behavior of inorganic semiconductors,the integrated PL intensity exhibits monotonic decrease with increasing temperature.A nonradiative path with characteristic activation energy of 8 meV is found to dominate at room temperature.The PL measurement also indicates that like in inorganic semiconductors,other types of excitation,for example,free carriers,could be responsible for the photoelectric processes.

纳米混合分子聚集体材料中弗兰克尔激子迁移的相位弛豫

在有机染料ＰＩＣⅠ中引入其衍生物ａｚａＰＩＣⅠ形成能量势垒，改变在混合分子聚集体中ＰＩＣⅠ的Ｊ聚集体的实体长度。用双调制外差检测的累积光子回波技术研究了相干弗兰克尔（Ｆｒｅｎｋｅｌ）激子失相过程。观测到激子失相时间Ｔ２随ａｚａＰＩＣⅠ克分子数的增大从６０ｐｓ变为２２４ｐｓ。这与在含能量陷阱的分子聚集体中激子失相时间Ｔ２随陷阱的增加而变短的现象刚好相反。

有机分子聚集体中振动分辨光谱的激子耦合效应（英文）

光谱是探究分子间相互作用及发光机理的有效手段.本工作采用Frenkel激子模型和量子力学/分子力学(QM/MM)方法系统研究了一系列聚集诱导发光(AIE)体系和传统荧光(非AIE)体系晶态下的吸收、发射光谱.结果表明,分子内电声子耦合(λ)与分子间激子耦合(J)竞争决定了晶态聚集体的光谱特性.在室温下,当J/λ值大于约0.17时,有机分子聚集体光谱的激子耦合效应将表现明显.例如,对于面对面排列的H聚集体,只有考虑激子耦合效应的理论计算光谱才与其实验光谱吻合很好,即相较于单分子光谱的吸收蓝移、发射减弱并红移.对于AIE体系,因为其J/λ值均小于0.17,AIE聚集体光谱特征主要是由分子内电声子耦合所主导,激子耦合可以忽略不计.