EXTRA-SHARC2 (Excited State Dynamics of Transition Metal Complexes using SHARC)

EXTRA-SHARC2提案旨在继续我们在SPP2102的合成和光谱合作伙伴所研究的过渡金属配合物的激发态动力学模拟的努力。为此，我们使用我们本地开发的激发态分子动力学SHARC方法。SHARC代表包括任意耦合在内的表面跳跃，能够在相同的基础上描述内部转换和系统间交叉。在第一个资助期，我们使用SHARC结合线性振动耦合（LVC）模型来参数化核动力学传播的势能面，从而可以非常有效地模拟全维度的大型复合体。在第二个资助期，预计将进一步采用这种方法（SHARC-LVC），并可能在有问题的情况下进行扩展。我们将努力处理具有开壳基态的分子，包括重态和四重态。我们的理论模拟有望提供具有原子分辨率的时间相关失活机制。通过这种方式，本项目将有助于合理设计地球上丰富的新型光敏剂和发光材料，并指导和预测控制配体解离或实现定向电子转移的策略，以用于多氧化还原反应。

The proposal EXTRA-SHARC2 is designed to continue our efforts in simulating the excited state dynamics of transition metal complexes investigated by synthetic and spectroscopic partners at the SPP2102. To this aim, we use our locally developed excited state molecular dynamics SHARC approach. SHARC stands for surface-hopping including arbitrary couplings and is able to describe internal conversion and intersystem crossing on the same footing. In the first funding period we employed SHARC combined with a linear vibronic coupling (LVC) model to parameterize the potential energy surfaces on which the nuclear dynamics is propagated, allowing for very efficient simulations of large complexes in full dimensionality. In the second funding period, this method (SHARC-LVC) is anticipated to be further employed and possibly extended in problematic cases. Effort will be put in dealing with molecules that possess an open-shell ground state, and involve doublet and quartet states. Our theoretical simulations are expected to deliver time-dependent deactivation mechanisms with atomistic resolution. In this way, this project will help rational design of novel Earth-abundant based photosensitizers and luminescent materials, as well as guide and predict strategies to control ligand dissociation or achieve directional electron transfer to be exploited in multiredox reactions.