Theory of interatomic (intermolecular) Coulombic decay in clusters

团簇中原子间（分子间）库仑衰变理论

• 批准号: 19146214
• 负责人: Professor Dr. Lorenz S. Cederbaum
• 金额: --
• 依托单位: Forschungsgruppe Theoretische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2005
• 资助国家: 德国
• 起止时间: 2004-12-31 至 2010-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/19146214?language=en
• 关键词: Theory; interatomic; intermolecular; Coulombic; decay

Interatomic (intermolecular) Coulombic decay (ICD) is an extremely efficient decay mode of inner-valence-ionized states in clusters, which has been predicted theoretically by the applicant and co-workers [Phys. Rev. Lett. 79, 4778 (1997)]. Recently, the theoretical findings of the Heidelberg group have found their full confirmation in a series of spectacular ICD experiments [1, 3, 4]. While most of the theoretical work performed on ICD dealt with establishing the generality and the mechanism of the phenomenon, the recent experimental and theoretical progress opens new horizons for the ICD research. The present proposal is aimed to provide theoretical answers for the most important open questions in the field. Among these are:How can one accurately calculate total and partial ICD rates in polyatomic and molecular clusters?What is the dependence of an ICD rate on the relative orientation of two (or more) cluster subunits if one (or more) of these subunits is a molecule?What is the effect of nuclear dynamics on ICD in polyatomic and molecular clusters?What is the effect of relativity (e.g., spin-orbit coupling) on ICD?What interatomic (intermolecular) decay processes, apart from ICD, can be observed in clusters?In order to answer the above questions, we propose to significantly improve the existing ab initio methodology for the calculation of energies and decay rates of the relevant electronic states of the ionized clusters as functions of the cluster geometry. In particular, we shall use the Green¿s function approach for the calculation of the decay rates. The results of the proposed theoretical research will be essential for interpreting and guiding the future ICD experiments.

原子间（分子间）库仑衰减（ICD）是集群中内价离子状态的极有效衰减模式，该模式已被适用的和同事[Phys [phys]预测理论上。莱特牧师。 79，4778（1997）]。最近，海德堡组的理论发现在一系列壮观的ICD实验中发现了他们的全部确认[1，3，4]。尽管在ICD上进行的大多数理论工作涉及建立现象的通用性和机制，但最近的实验和理论进步为ICD研究开辟了新的视野。目前的建议旨在为该领域最重要的开放问题提供理论答案。其中包括：一个人如何准确计算多原子和分子簇中的总和部分ICD速率？ICD速率对两个（或更多）亚基的相对方向的依赖性是什么（如果这些亚基中的一个（或更多）分子是分子？在ICD上的耦合？除了ICD之外，可以在集群中观察到哪些原子间（分子间）衰减过程？为了回答上述问题，我们建议可以显着提高现有的从头算法来计算能量的现有方法，以计算电离簇的相关电子状态的衰减速率，包括电离簇的相关电子状态，作为函数的函数cl clementer gelementer gememess。特别是，我们将使用绿色的功能方法来计算衰减率。所提出的理论研究的结果对于解释和指导未来的ICD实验至关重要。