Development of new quantum-chemical methods for the description of static correlation effects

静态关联效应在量子化学中非常重要，例如用于描述键断裂或金属系统。拟议的项目涉及开发新的量子化学方法来描述这些效应。它计划结合联合收割机的波函数的广义耦合集群扩展的同时优化的基础单电子轨道。随着大尺度应用的发展，动力学关联效应的微扰展开式有待进一步发展。在将上述思想作为有效的计算机代码实现之后，这些发展的益处将通过在以下系统上的示例应用来证明：（a）反应机理（羧基自由基的衰变），（B）过渡金属化学（与过渡金属原子的基元反应）和（c）分子导体（硫-氮化物-低聚物）。

Static correlation effects are of great importance in quantum chemistry, e.g. for the description of bond breaking or metallic systems. The proposed project deals with the development of new quantum chemical methods to describe these effects. It is planned to combine a generalized coupled-cluster expansion of the wavefunction with a simultaneous optimization of the underlying one-electron orbitals. With the scope of large scale applications, perturbation expansions for dynamic correlation effects are to be developed. After implementation of the above ideas as an efficient computer code, the benefit of these developments shall be demonstrated with sample applications on the following systems: (a) Reaction mechanisms (decay of carboxyl radicals), (b) transition metal chemistry (elementary reactions with transition metal atoms) and (c) molecular conductors (sulfur-nitride-oligomers).