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)库仑衰变(ICD)是团簇内价电离态的一种非常有效的衰变方式，申请者和同事从理论上预测了ICD的存在。莱特牧师。79,4778(1997)]。最近，海德堡小组的理论发现在一系列壮观的ICD实验中得到了充分的证实[1，3，4]。虽然大多数关于ICD的理论工作都是为了建立这种现象的共性和机制，但最近的实验和理论进展为ICD的研究开辟了新的视野。本提案的目的是为该领域最重要的未决问题提供理论答案。其中包括：如何准确计算多原子和分子团簇的总ICD速率和部分ICD速率？如果这些亚基中的一个(或多个)是分子，ICD速率与两个(或多个)团簇亚基的相对取向有什么关系？多原子和分子团簇中的核动力学对ICD有什么影响？相对论(例如，自旋-轨道耦合)对ICD有什么影响？除了ICD，团簇中还可以观察到哪些原子间(分子间)衰变过程？为了回答上述问题，我们建议显著改进现有的从头计算方法，用于计算作为团簇几何函数的电离团簇的相关电子态的能量和衰减率。特别是，我们将使用格林-S函数方法来计算衰减率。所提出的理论研究结果将对解释和指导未来的ICD实验至关重要。