二氧化钛分子电致发光激发特性研究

采用密度泛函B3P86方法优化得到了沿分子平面不同外电场作用下TiO₂分子的基态稳定构型, 在优化构型下利用杂化CIS (CI-Singles)-B3P86方法在6-311＋G*基组水平上, 研究了不同外电场下TiO₂分子前六个激发态的激发能和跃迁波长等激发特性. 研究结果表明, TiO₂分子多个激发态满足偶极跃迁定则, 跃迁光谱对应多个峰值, 在分子水平上, 可以增大利用太阳光的比例. 在外电场作用下, 能隙随电场的增大而减小, 电子易从最高占据轨道跃迁到最低空轨道形成空穴, 各个激发态跃迁波长均有随电场增大发生红移的趋势, 最长589 nm, 因而利用外电场可以控制材料的发光光谱范围在可见光区域扩展.     

SAC-CI方法研究甲基乙烯基硅酮分子激发态11A″,11A′,21A″结构与性质

采用对称性匹配簇/组态相互作用(symmetry adapted cluster-configuration interaction,SAC-CI)方法,在6-311++g**基组水平上优化了甲基乙烯基硅酮分子的前三个单激发态11A″,11A′,21A″的平衡几何结构,比较三个激发态的电荷分布,最高占据轨道,最低空轨道,能隙等结构特性.研究发现,11A′态能隙差最小,电子容易发生跃迁.计算了三个单重激发态相应的振动光谱,得出其振动模式.从甲基乙烯基硅酮分子激发态结构特性,电荷分布,极强位置振动模式等方面分析了其断键机制.     

Properties of a Si2N molecule under an external electric field

In the present work,we adopt the ccsd/6-31g（d） method to optimize the ground state structure and calculate the vibrational frequency of the Si2N molecule.The calculated frequencies accord satisfactorily with the experimental values,which helps confirm the ground state structure of the molecule.In order to find how the external electric field affects the Si2N molecule,we use the density functional method B3P86/6-31g（d） to optimize the ground state structure and the time-dependent density functional theory TDDFT/6-31g（d） to study the absorption spectra,the excitation energies,the oscillator strengths,and the dipole moments of the Si2N molecule under different external electric fields.It is found that the absorption spectra,the excitation energies,the oscillator strengths,and the dipole moments of the Si2N molecule are affected by the external electric field.One of the valuable results is that the absorption spectra of the yellow and the blue-violet light of the Si2N molecule each have a red shift under the electric field.The luminescence mechanism in the visible light region of the Si2N molecule is also investigated and compared with the experimental data.     

SiN分子外电场情况下的发光特性

为全面分析外电场对分子发光特性的影响, 本文采用密度泛函B3P86方法6-31g(d)基组, 对SiN分子进行了基态结构的优化, 进而使用含时密度泛函方法(time dependent density functional theory, TDDFT), 计算了不同方向及大小的外电场情况下SiN分子的吸收谱、激发能、振子强度、跃迁偶极矩. 通过比较发现外电场对该分子的激发能、吸收谱、跃迁振子强度及跃迁偶极矩影响都比较明显, 说明了电场对SiN分子的激发特性影响比较复杂, 特别是在加场前后分子均有在可见光区波段的吸收谱, 这对研究分子的发光很有意义.同时对该分子所发可见光谱的产生机理进行了分析, 并与已有实验结果进行比较.     

Properties of a Si₂N molecule under an external electric field

In the present work,we adopt the ccsd/6-31g(d) method to optimize the ground state structure and calculate the vibrational frequency of the Si2N molecule.The calculated frequencies accord satisfactorily with the experimental values,which helps confirm the ground state structure of the molecule.In order to find how the external electric field affects the Si2N molecule,we use the density functional method B3P86/6-31g(d) to optimize the ground state structure and the time-dependent density functional theory TDDFT/6-31g(d) to study the absorption spectra,the excitation energies,the oscillator strengths,and the dipole moments of the Si2N molecule under different external electric fields.It is found that the absorption spectra,the excitation energies,the oscillator strengths,and the dipole moments of the Si2N molecule are affected by the external electric field.One of the valuable results is that the absorption spectra of the yellow and the blue-violet light of the Si2N molecule each have a red shift under the electric field.The luminescence mechanism in the visible light region of the Si2N molecule is also investigated and compared with the experimental data.     

Si2O2 molecule: structure of ground state and the excited properties under different external electric fields

Geometry and vibrational frequencies of the ground state of Si 2 O 2 molecule are studied using density function theory (DFT) at the level of cc-pvtz and 6-311++G.It is found that the optimizing value by B3lyp/cc-pvtz is closer to the experimental data.The excited properties under different external electric fields are also investigated by the time-dependent-DFT method.Transitions from the ground state of Si 2 O 2 molecule to the first singlet state under different external electric fields can take place more easily.The corresponding absorption spectral line is about 360 nm in wavelength and the excitation energy is about 3.4 eV.     

SAC-CI方法研究甲基乙烯基硅酮分子激发态1 1A’’, 1 1A’, 2 1A’’结构与性质

采用对称性匹配簇/组态相互作用(symmetry adapted cluster－configuration interaction, SAC－CI)方法, 在6-311++g**基组水平上优化了甲基乙烯基硅酮分子的前三个单激发态1 1A’’, 1 1A’, 2 1A’’的平衡几何结构, 比较三个激发态的电荷分布, 最高占据轨道, 最低空轨道, 能隙等结构特性. 研究发现, 1 1A’ 态能隙差最小, 电子容易发生跃迁. 计算了三个单重激发态相应的振动光谱, 得出其振动模式. 从甲基乙烯基硅酮分子激发态结构特性, 电荷分布, 极强位置振动模式等方面分析了其断键机制.     

Si3O cluster: excited properties under external electric field and oxygen-deficient defect models

This paper investigates the excited states of Si₃O molecule by using the single-excitation configuration interaction and density functional theory. It finds that the visible light absorption spectrum of Si₃O molecule comprises the yellow and the purple light without external electric field, however all the visible light is included except the green light under the action of external electric field. Oxygen-deficient defects, which also can be found in Si₃O molecule, have been used to explain the luminescence from silicon-based materials but the microstructures of the materials are still uncertain. Our results accord with the experimental values perfectly, this fact suggests that the structure of Si₃O molecule is expected to be one of the main basic structures of the materials, so the oxygen-deficient defect structural model for Si₃O molecule also has been provided to research the structures of materials.     

光功能导向的SiNN分子电致发光特性研究

采用优选出的密度泛函B3P86/cc-PVTZ方法对SiNN分子进行了基态结构的优化,然后使用含时密度泛函方法(Time-dependent density functional theory,TDDFT)计算了SiNN分子前7个激发态的激发能,吸收谱,跃迁振子强度等激发特性,进而在得到不同外电场下SiNN分子的基态稳定结构的基础上,研究了外电场作用下SiNN分子的激发特性.与无电场时的激发特性进行比较发现SiNN分子的激发能,吸收谱,跃迁振子强度在外电场作用下变化明显,特别是加场后使原来跃迁禁戒的能级之间发生了跃迁,出现了紫光区的376～401 nm波长的吸收谱,电子在各能级之间的跃迁能力也发生了很大改变.同时对SiNN分子可见光谱的产生机理也进行了分析,经理论分析发现SiNN分子有可见光波段的发射谱且数值与实验测量结果非常吻合.