Advanced concepts in vibrational configuration interaction theory (VCI)

振动构型相互作用理论 (VCI) 的先进概念

• 批准号: 404988685
• 负责人: Professor Dr. Guntram Rauhut
• 金额: --
• 依托单位: Institut für Theoretische Chemie (ITheoC)
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2018
• 资助国家: 德国
• 起止时间: 2017-12-31 至 2022-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/404988685?language=en
• 关键词: Advanced; concepts; vibrational; configuration; interaction

The variational calculation of anharmonic vibrational frequencies of molecules and molecular clusters has gained considerable interest in the recent past. However, the methods employed face two computational bottlenecks, i.e. the accurate calculation of a multidimensional potential energy surface by sophisticated electronic structure methods and the account of vibration correlation effects. This proposal focuses on the latter aspect and new ideas are presented, which aim at the reduction of the computational cost and memory requirements as well as a balanced treatment of molecules with quasi-degenerate vibrational states. Essentially, a new configuration selective multistate vibrational configuration interaction program shall be developed, which allows for the balanced calculation of larger systems than the present code and which is not limited in any expansion orders of the correlation space and the representation of the potential energy surface. Once the new program is operative, it shall be applied to state-of-the-art problems in vibrational spectroscopy and the investigation of metal halide, (MX)_n, clusters with up to 20 atoms.

近年来，分子和分子团簇非简谐振动频率的变分计算引起了人们极大的兴趣。然而，所采用的方法面临两个计算瓶颈，即精确计算的多维势能面的复杂的电子结构方法和帐户的振动相关效应。该建议侧重于后者，提出了新的想法，其目的是减少计算成本和内存需求，以及平衡处理的准简并振动态的分子。从本质上讲，应开发一个新的配置选择性的多态振动组态相互作用程序，它允许平衡计算比目前的代码更大的系统，它不限于任何扩展的相关空间的顺序和势能面的表示。新程序一旦投入运行，将应用于振动光谱学中的最新问题和20个原子以下的金属卤化物（MX）_n团簇的研究。