巨大有機分子の光化学物性を扱うための励起状態分子動力学法の開発

开发处理有机大分子光化学性质的激发态分子动力学方法

基本信息

批准号：
12F02333
负责人：
IRLE Stephan (2013)
金额：
$ 0.51万
依托单位：
Nagoya University
依托单位国家：
日本
项目类别：
Grant-in-Aid for JSPS Fellows
财政年份：
2012
资助国家：
日本
起止时间：
2012 至 2013
项目状态：
已结题

项目摘要

We employed simulations based on density functional theory (DFT) and density functional tight binding (DFTB) to characterize structural and electronic properties of self-assembling organic molecular architectures of several varieties. In a flexible organic chromophore developed by collaborators in the Yamaguchi group, we identified a correlation between calculated excited state redshifts and experimental fluorescence wavelgenths, supporting the hypothesis of excimer formation in the excited state. We also showed through periodic DFTB simulations that small intercalating molecules can effectively tune the band gap in covalent organic frameworks.Furthermore, direct dynamics simulations of C_2 loss in C_<62> and C_<72> fullerenes support the proposed size-down synthesis mechanism as the final step of C_<60> and C_<70> fullerene formation. We also studied the effect of intermolecular stacking on aromaticity in porphyrinoid complexes to demonstrate that the stability of a formally antiaromatic, recently synthesized Ni(II) norcorrole is due to a reduction in antiaromaticity upon stacking, rather than a metal-metal bonding effect. Finally, to develop a fuller understanding of how intermolecular interactions alter excited state properties in organic molecules, we developed and implemented a new strategy called △DFTB to rapidly evaluate excited state energies and forces.

我们采用基于密度功能理论（DFT）和密度功能紧密结合（DFTB）的模拟来表征几种变体的自组装有机分子体系结构的结构和电子特性。在Yamaguchi组的合作者开发的柔性有机色团中，我们确定了计算的激发态红移与实验荧光Wavergenths之间的相关性，从而支持激发态以激发态形成的假设。我们还通过周期性的DFTB模拟表明，小的互插分子可以有效地调节带隙在共价有机框架中。furthermore，C_2中C_2损耗的直接动力学模拟，C_ <62>和C_ <72> fullerenes fullerenes支持了所提出的大小合成机制，作为C_ <60> <60> <70> <60> <70的最终步骤。我们还研究了分子间堆叠对卟啉素复合物中芳香族性的影响，以证明正式抗抗抗神经，最近合成的Ni（ii）Norcorrole的稳定性是由于堆叠时抗脉络膜的降低，而不是金属金属键效应。最后，为了对分子间相互作用如何改变有机分子的激发态性质有更深入的了解，我们制定并实施了一种称为△dftb的新策略，以快速评估激发态能量和力。