Intermolecular Coulombic Decay in Biological Systems and Open-Shell Species

该项目旨在开发高效的计算工具，用于研究大分子体系中电离和激发诱导的ICD，并将其应用于光解酶中初始的光诱导电子转移步骤以及溶剂化的氨基酸和核碱基。为此，我们计划结合复杂吸收势技术，利用局部轨道和自旋分量标度等现代数值技术，实现激发和电离代数图解构建方案。这些程序将被用来首次证明ICD是DNA光解酶中电子生成的功能机制，它启动了光损伤DNA的修复。与Hergenhahn和Winter的实验组携手合作，将研究溶剂化氨基酸和核碱基中的ICD，例如ICD效率对簇大小、激发能氢键的依赖。这些发现可以预期对自然界低能电子产生的基本理解产生直接影响，从而对辐射引起的生物组织损伤产生影响。

The proposed project aims at the development of efficient computational tools for the investigation of ionization and excitation induced ICD in large molecular systems and their application to the initial, photo-induced electron transfer step in photolyases as well as to solvated amino acids and nucleobases. For this objective, we plan to implement excitation and ionization algebraic diagrammatic construction schemes in combination with the complex absorbing potential technique, exploiting modern numerical techniques like local orbitals and spin-component scaling. These programs will then be employed to demonstrate for the first time ICD to be a functional mechanism in the electron generation in DNA photolyases, which initiates repair of photo-damaged DNA. Hand in hand with the experimental groups of Hergenhahn and Winter, ICD in solvated amino acids and nucleobases will be investigated, such as the dependence of ICD efficiency on cluster size, hydrogen bonds of excitation energy, for example. These findings can be expected to have an immediate impact onto the fundamental understanding of low-energy electron generation in nature and hence of radiation-induced damage in biological tissue.