Institut für Physik, Universität Rostock, D-18051 Rostock, Germany.
J Phys Chem A. 2012 Nov 26;116(46):11451-8. doi: 10.1021/jp3069706. Epub 2012 Sep 19.
Quantum chemical and quantum dynamical calculations are performed for a bay-substituted perylene bisimide dye up to its hexameric aggregate. The aggregate structure is determined by employing the self-consistent charge density functional tight-binding (SCC-DFTB) approach including dispersion corrections. It is characterized by a stabilization via two chains of hydrogen bonds facilitated by amide functionalities. Focusing on the central embedded dimer, the Coulomb coupling for this J-aggregate is determined by means of the time-dependent density functional theory (TDDFT) to be -514 cm(-1). Exciton vibrational coupling is treated within the shifted oscillator model from which five strongly coupled modes per monomer are selected for inclusion into a minimal dynamic model. Performing wave packet propagations for a model employing up to 7 electronic states and 30 vibrational modes using the multiconfiguration time-dependent Hartree method, aggregate absorption spectra are obtained and compared to experiment.
对一个取代基位于萘并咪唑染料的 bay 位的染料进行了量子化学和量子动力学计算，直至其六聚体聚集态。采用自洽电荷密度泛函紧束缚（SCC-DFTB）方法，包括色散校正，确定了聚集态结构。酰胺官能团促进了两条氢键链的形成，从而实现了稳定化。聚焦于中心嵌入的二聚体，通过含时密度泛函理论（TDDFT）确定了这种 J-聚集体的库仑耦合为-514 cm(-1)。用位移振荡器模型处理激子振动耦合，从每个单体中选择五个强耦合模式纳入最小动态模型。采用多组态含时哈特ree 方法对一个最多包含 7 个电子态和 30 个振动模式的模型进行波包传播，得到了聚集态吸收光谱，并与实验进行了比较。
