多尺度体系的构效关系及激子动力学的理论研究化学物理专业论文.docxVIP

摘要体在不同温度下的吸收和发射光谱。我们发现其光谱行为跟多聚体的聚合方式 摘要 体在不同温度下的吸收和发射光谱。我们发现其光谱行为跟多聚体的聚合方式 密切相关。我们研究了两种类型的多聚体，每种类型都对从三聚体到七聚体进 行了研究。红荧烯晶体沿着b方向的聚合方式是H型聚合，在低温下，发射谱中 的0．O峰是看不到的，当温度升高时，0．0峰逐渐出现；红荧烯晶体沿着c方向的 聚合方式是J型聚合，低温时发射谱中的0．O峰强度反而比高温时要大。我们以 二聚体为例，发现激子态的对称性是造成上述光谱行为的根本原因。 3．用Frenkel激子．电荷转移激子混合模型结合长程修正的含时密度泛函理论 研究了H型花酰亚胺染料分子聚合物的的低位激发态的性质11彳发现实验上观测 到的2-3 eV附近的低能吸收峰对应的是一个混合激子态。当多聚体中包含四到 五个分子时，我们用混合激子模型成功地重复出了由PBI堆垛而产生的光学性 质的变化趋势，如吸收带的蓝移、发射谱的大的Stokes位移等。 关键词：多聚体，密度泛函理论，含时密度泛函理论，长程修正的含时密度泛 函理论，限制性密度泛函理论，振动分辨的吸收和发射谱，良Ill【el激子，电荷 转移激子，激子耦合，电子转移积分，空穴转移积分 邶STRACTABSTRACT 邶STRACT ABSTRACT In this thesis，I present my major works during the period of my Phi)study．In the past years，I focus my research on developing methods to calculate the electronic structure and spectral properties of systems with different sizes．This thesis just gives a description of these methods．For small molecules，we can employ high accurate ab inifio or first-palnciples methods to gain the information needed to calculate the spectra；While for aggregates，wavefunction-based methods or density functional the— ories ale too expensive，SO we have to employ effective model Hamiltonians，where the microscopic parameters Can be determined through high accurate quantum chemistry calculations whatever the Hamiltonians are．The following is a brief introduction to these methods： 1．For small molecules，the displaced harmonic oscillator model and the anhar- monic oscillator model are employed to treat the intramolecular harmonic vibrational modes and anharmonic one．s，respectively．In the first model，the optimal geometries and vibrational frequencies of the ground and excited states needed as input ale pro— duced by ab initio methods(HF／CIS)or first-principles methods(DFT／TDD网；In the second model，two time—independent Schrbdinger equations are solved numerically, where the anhamonic potential energy curves of the ground and excited states ale from quantum chemistry calculations as well． 2．瞩／hen the intermolecular distance is large or the intcn