C-Photo: Computational photochemistry and in silico design of MOST systems

C-Photo：计算光化学和 MOST 系统的计算机设计

• 批准号: 517844450
• 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 Units
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/517844450?language=en
• 关键词: Photo; Computational; photochemistry; silico; design

The utilization of solar energy is the most promising pathway to cover the energy demands of our modern society. A largely unexplored concept is in this context the molecular solar thermal (MOST) energy conversion process, which releases heat through photochemically triggered chemical transformations on demand. In the proposed research unit FOR MOST, this concept is to be explored from a fundamental research point of view in concert of synthesis, spectroscopy, theory and application. This proposal covers the theoretical part with emphasis on the photochemical and spectroscopical aspects. In detail, genetic algorithms and machine learning approaches will be used to explore the vast chemical space of different MOST systems by pre-screening for the most promising MOST molecules, so-called mostophores. Further detailed quantum chemical investigations using our self-developed excited-state methods but also all other available theoretical tools complement the efforts. The “best” candidates will then be synthesized and spectroscopically investigated with focus on optimal MOST properties, for example, a high energy-to-mass ratio, favorable overlap with the solar spectrum and appropriate storage times together with the other FOR MOST partners. Within this project, we will investigate in detail the photochemical switching mechanisms into the storage state of coupled azobenzenes, azaborines and norbornadiene as well as of hybrid systems. We will thereby help to design novel mostophores by a priori in silico design, by straightforward derivatization as well as by exploitation of molecular interactions for the stabilization of the storage state. A further important contribution of this project is the simulation of optical spectra of the mostophores in their molecular environments to guide the interpretation of static and time-resolved experimental spectra using our self-developed quantum chemical methodology and environment models. Along the same lines, we will investigate the possibility of oxidative and/or reductive switching of the mostophores, i.e. by electron detachment and attachment. The switching mechanisms will be computed and electronic spectra of the intermediates will be simulated to guide experimental investigations. The theoretical efforts undertaken in this project are thus well embedded into the FOR MOST research unit and will contribute substantially the collaborative projects.

太阳能的利用是满足现代社会能源需求的最有前途的途径。在这种情况下，一个在很大程度上未被探索的概念是分子太阳能(MOST)能量转换过程，该过程通过光化学触发的化学转换释放热量。在MOST拟议的研究单位中，这一概念将从基础研究的角度进行探索，综合、光谱学、理论和应用。这项建议涵盖了理论部分，重点放在光化学和光谱方面。具体地说，遗传算法和机器学习方法将被用来探索不同MOST系统的广阔化学空间，方法是预先筛选最有前途的分子，即所谓的最多分子。使用我们自己开发的激发态方法以及所有其他可用的理论工具进行进一步的详细量子化学研究是对这一努力的补充。然后，将合成“最佳”候选者，并对其进行光谱研究，重点是最优的性质，例如，高能量质量比、与太阳光谱有利的重叠以及与其他候选者一起为大多数合作伙伴提供适当的储存时间。在这个项目中，我们将详细研究偶氮苯、偶氮硼和降冰片二烯以及杂化体系的光化学转换机制。因此，我们将通过在电子设计中的先验，通过直接的衍生化以及通过利用分子相互作用来稳定存储状态，来帮助设计新的分子轨道。该项目的另一个重要贡献是模拟了分子环境中更多分子的光谱，以指导使用我们自己开发的量子化学方法和环境模型来解释静态和时间分辨的实验光谱。沿着同样的思路，我们将研究更多基团的氧化和/或还原开关的可能性，即通过电子脱离和附着。将计算开关机制，并模拟中间体的电子光谱以指导实验研究。因此，在该项目中进行的理论努力很好地融入了For MOST研究单位，并将对合作项目作出重大贡献。