在最小的PPE树枝状聚合物结构单元中不寻常的斯托克斯位移：电子振动对称性对能带起源的作用？
On the unusual Stokes shift in the smallest PPE dendrimer building block: Role of the vibronic symmetry on the band origin?
摘要：
1，3-双（苯乙炔基）苯是光捕获聚亚苯基乙炔（PPE）树枝状聚合物的主要发色团。实验上已知它与它的一对二苯基乙炔（aka）共享相同的吸收光谱。二苯乙炔）间位取代的支链，但在其发射光谱中相对于其带源（对应于反对称炔属伸缩内一个振动量子的损失）表现出约2000 cm $^{-1}$的不寻常斯托克斯位移。我们建议在目前的工作中不寻常的，但似乎合理的参与分子对称性选择规则的情况下，玻恩-奥本海默近似是远远有效的。我们的假设是安慰与量子动力学（MCTDH）模拟的吸收和发射紫外-可见光谱的基础上的量子化学（TD-DFT）数据和非绝热振动耦合哈密顿模型。
英文摘要：
1,3-bis(phenylethynyl)benzene is the primary chromophore of light-harvesting polyphenylene ethynylene (PPE) dendrimers. It is experimentally known to share the same absorption spectrum as its pair of diphenylacetylene (aka. tolane) meta-substituted branches, yet exhibits an unusual Stokes shift of about 2000 cm$^{-1}$ with respect to its band origin (corresponding to the loss of one vibrational quantum within the antisymmetric acetylenic stretching) in its emission spectrum. We suggest in the present work the unusual but plausible involvement of molecular symmetry selection rules in a situation where the Born-Oppenheimer approximation is far to be valid. Our hypothesis is comforted with quantum dynamics (MCTDH) simulations of absorption and emission UV-visible spectra based on quantum chemistry (TD-DFT) data and a diabatic vibronic coupling Hamiltonian model.
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