Quantum mechanical investigations of the thermodynamic and kinetic properties of H2-activating chemical systems with accurate first-principles wave-function and density based computational methods

使用精确的第一原理波函数和基于密度的计算方法对 H2 活化化学系统的热力学和动力学性质进行量子力学研究

• 批准号: 153069439
• 负责人: Professor Dr. Stefan Grimme
• 金额: --
• 依托单位: Mulliken Center for Theoretical Chemistry
• 依托单位国家: 德国
• 项目类别: Research Units
• 财政年份: 2009
• 资助国家: 德国
• 起止时间: 2008-12-31 至 2013-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/153069439?language=en
• 关键词: Quantum; mechanical; investigations; thermodynamic; kinetic

The thermodynamic and kinetic properties of H2-activating chemical systems will be investigated by accurate first-principles wave-function and density based (DFT) quantum chemical methods. The determination of H2 complexation sites, their geometries and interaction energies (including computation of van der Waals type complexes) is the initial step in all treatments. Special attention will be brought to the effects of thermal (entropic) corrections as well as the influence of solvation effects. For the interesting (reactive) cases searches for transition states, determination of the thermodynamics, computation of IR spectra, and various analysis techniques are applied. By the combination of accurate DFT-D3 gas phase and COSMORS solvation data, reliable free reaction enthalpies are computed for the first time for complex H2-activating species that can be directly compared to experimentally observed quantities. Beside methodological insight regarding the applied quantum chemical methods, the project opens the chance to develop a detailed view of hydrogen activation mechanisms and the structural factors that influence the course of the various reactions under realistic conditions. All investigations will be carried out in close collaboration with the experimental groups.

H2激活化学系统的热力学和动力学特性将通过准确的第一原理波功能和基于密度（DFT）量子化学方法研究。 H2络合位点的测定，它们的几何形状和相互作用能（包括范德华类型复合物的计算）是所有处理的第一步。将特别注意热（熵）校正以及溶剂化效应的影响。对于有趣的（反应性）案例搜索过渡状态，应用热力学，IR光谱的计算以及各种分析技术。通过准确的DFT-D3气相和宇宙溶剂化数据的组合，可以首次计算可靠的自由反应焓用于复杂的H2激活物种，这可以直接与实验观察到的数量进行比较。除了有关应用的量子化学方法的方法论洞察力外，该项目还开辟了机会，开发了对氢气激活机制的详细观点以及在现实条件下影响各种反应过程的结构因素。所有调查将与实验组密切合作进行。