AI 中文总结
该研究通过线性Jahn-Teller模型推导半整数拓扑不变量，结合表面跳跃模拟发现，分子锥形交叉的非平凡拓扑会改变相同本征面的跳跃速率，拓展了拓扑对分子激发态动力学的影响范围。
AI 中文摘要
避免交叉和锥形交叉（CI）的电子结构拓扑是不同的，后者的特征是电子波函数中存在几何相位。利用线性Jahn-Teller模型，我们表明通过在哈密顿量中添加Pauli σ_y项，可以从锥形交叉生成避免交叉，同时保留后者的非平凡拓扑。类似于固态系统，我们将半整数拓扑不变量推导为CI核分支空间上贝里曲率的积分。我们通过开展最少跳跃面跳跃模拟研究电子拓扑对化学动力学的影响，发现在相同本征面上但具有不同拓扑的跳跃速率存在差异。我们的工作将拓扑对分子激发态动力学的影响范围从可通过电子-核和自旋-轨道耦合实际实现的贝里相位之外进行了拓展。
英文摘要
The topology of the electronic structure for an avoided crossing and a conical intersection (CI) is different and is characterized by the presence of the geometric phase in the electronic wavefunction in the latter. Using the linear Jahn-Teller model, we show that an avoided crossing can be created from the conical intersection while preserving the nontrivial topology of the latter by adding a Pauli $σ_y$ term to the Hamiltonian. Analogously to solid state systems, we derive a half-integer topological invariant as the integral of the Berry curvature over the CI nuclear branching space. We investigate the influence of electronic topology on chemical dynamics by conducting fewest-switches surface hopping simulations and find distinct hopping rates on identical eigensurfaces but with different topologies. Our work extends the influence of topology on molecular excited state dynamics beyond the Berry phase that can be practically realized through electron-nuclear and spin-orbit coupling.
