Photo-induced non-adiabatic dynamics of Carotenoids: a systematic investigation of small model systems towards the biological molecule

类胡萝卜素的光诱导非绝热动力学：对生物分子小模型系统的系统研究

• 批准号: 468734905
• 负责人: Professor Dr. Andreas Dreuw
• 金额: --
• 依托单位: Chair of Theoretical and Computational Chemistry
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/468734905?language=en
• 关键词: Photo; induced; non; adiabatic; dynamics

Carotenoids are central building blocks of natural photo-active pigment proteins. Their molecular structure is dominated by a conjugated polyene chain and they possess passive as well as active biological functions. In plant and bacterial light harvesting complexes, carotenoids act as protecting pigments by quenching reactive singlet and triplet states thereby preventing the generation of harmful singlet oxygen. However, until today the mechanistic details of these biological functions, even the energetic order as well as decisive properties of the relevant electronic states are yet highly debated. Within this project we aim at closing this knowledge gap.In a systematic theoretical study of the electronic structure and the nuclear dynamics we first aim at investigating medium long polyenes quantum mechanically before we turn to longer ones. Besides the linear polyenes with increasing number of conjugated double bonds, we plan to systematically study also the influence of their methyl substitution on the photochemical processes. Thereby, important insights will be gained into the photochemistry of polyenes themselves, however, with the help of these results quantum chemical methods will be developed further to open a viable way to the quantitative description of the electronic structure of carotenoids and the semi-classical simulation of their excited state dynamics.Our outlined systematic project will, in the long run, lead to a fundamental understanding of the photochemistry of the biologically utterly important Carotenoids and eventually close the existing knowledge gap.

类胡萝卜素是天然光活性色素蛋白的核心组成部分。它们的分子结构以共轭多烯链为主，具有被动和主动的生物学功能。在植物和细菌的捕光复合体中，类胡萝卜素通过猝灭反应的单线态和三线态而起到保护色素的作用，从而防止有害单线态氧的产生。然而，直到今天，这些生物功能的机制细节，甚至相关电子态的能量顺序和决定性性质仍然存在着激烈的争论。在这个项目中，我们的目标是缩小这一知识差距。在对电子结构和核动力学的系统理论研究中，我们首先旨在从量子力学角度研究中长多烯，然后再转向较长的多烯。除了增加共轭双键数目的线型多烯外，我们还计划系统地研究它们的甲基取代对光化学过程的影响。因此，我们将对多烯化合物本身的光化学有重要的了解，然而，在这些结果的帮助下，量子化学方法将进一步发展，为定量描述类胡萝卜素的电子结构和半经典的激发态动力学模拟开辟一条可行的途径。从长远来看，我们概述的系统工程将导致对生物上绝对重要的类胡萝卜素的光化学的基本理解，并最终弥合现有的知识差距。