Non-adiabatic quantum molecular dynamics of complex systems

质子的非绝热跃迁和量子力学隧穿是化学和生化系统中的重要过程。用非绝热量子动力学方法描述复杂系统中的这类过程是本项目的目的。在过去的十年中，环-聚合物分子动力学(RPMD)方法已被证明是近似量子动力学模拟的有用工具。非绝热过程不能直接用RPMD方法来描述，但最近有人提出了一种扩展的RPMD方法来模拟两态非绝热过程，即动力学约束(KC)RPMD。该项目旨在推广和进一步发展KC-RPMD方法。此外，该方法将被用于研究复杂系统中化学和生物化学上重要的非绝热过程。可以考虑几个显示电子转移过程(ET)或质子耦合电子转移过程(PCET)的生物无机体系：基于双(咪唑)四苯基铁卟啉的配合物、天青蛋白、三(膦)硼烷支撑的铁配合物、具有轴向碳供体的三(膦)烷基配体的铁配合物、与二乙二酮肟配体的钴配合物。

Non-adiabatic transitions and quantum mechanical tunneling of protons are important processes in chemical and biochemical systems. The description of such processes in complex systems using non-adiabatic quantum dynamics methods is the aim of this project. In the last decade the ring-polymer molecular dynamics (RPMD) approach has shown to be a useful tool for approximate quantum dynamics simulations. Non-adiabatic processes cannot be described using the RPMD approach directly, but an extension of the RPMD approach to simulate two-state non-adiabatic processes, the kinetically constrained (KC) RPMD, was proposed very recently. The project aims to generalize and further develop the KC-RPMD approach. Furthermore, the approach will be used to investigate chemically and biochemically important non-adiabatic processes in complex systems. Several bioinorganic systems showing electron transfer processes (ET) or proton coupled electron transfer processes (PCET) can be considered: complexes based on Bis(imidazole) Iron Tetraphenylporphyrins, azurin proteins, a tris(phosphine)borane-supported iron complex, iron complexes with tris(phosphino)alkyl ligands featuring an axial carbon donor, cobalt complexes with diglyoxime ligands.