Non-adiabatic dynamics of electronically excited linear polyenes: learning from small and medium-sized for long polyenes and their biological function

本项目的目标是实现对线型多烯的光化学的全面的理论描述，线型多烯是最重要的分子类之一，因为它们在材料科学、化学和生物学中充当生色团的模型。直到今天，人们对它们的光化学性质还知之甚少，并且仍然是有争议的讨论对象。从理论上看，这种缺乏理解的根源在于与多烯的光化学相关的电子态的不同和困难的电子结构。因此，在这个项目中，我们结合了两位研究人员的专业知识，提供了量子化学方法来可靠地计算最小到中等大小的多烯的相关电子态，并从量子力学的角度模拟了光致核动力学。由于这一建议的基本概念，从最小的多烯丁二烯开始，然后系统地进行到更大的多烯丁二烯，可以推导出基本的光化学原理，并可以解释实验观察到的线性多烯的光化学趋势。基于这种深刻的理解，改进的材料可以设计用于技术应用。

The goal of this project is to achieve a comprehensive theoretical description of the photochemistry of linear polyenes, which represent one of the most important molecular classes, since they serve as models for chromophores in material science, chemistry as well as biology. Until today, their photochemical properties are only poorly understood and still subject of controversial discussions. From a theoretical point of view, the origin for that lack of understanding lies in the different and difficult electronic structure of the electronic states relevant for the photochemistry of polyenes. Within this project, we thus combine the expertise of two researchers to provide quantum chemical approaches to compute reliably the relevant electronic states of the smallest up to medium-sized polyenes, and in addition to simulate the photo-induced nuclear dynamics quantum mechanically. Owing to the underlying concept of this proposal, to start with the smallest polyene butadiene and then to systematically proceed to larger ones, basic photochemical principles can be derived and the experimentally observed trends in the photochemistry of linear polyenes can be explained. Based on such a deep understanding, improved materials can be designed for use in technological applications.