论文标题
与浆果伪磁场的对称过渡状态后分叉反应
Symmetric Post-Transition-State Bifurcation Reactions with Berry Pseudo-Magnetic Fields
论文作者
论文摘要
我们研究了电子退化和自旋轨道耦合（SOC）引起的浆果力（即在核上起作用的伪磁力，可能会改变过渡后状态分叉（PTSB）反应路径（PTSB）反应路径，并在多个产物共享相同过渡状态时影响情况的产品选择性。为了估计这种效果的幅度，在存在磁场（模拟浆果曲率）的情况下，在具有山谷 - ridge拐点（VRI）点的模型系统上执行Langevin动力学。我们还为这种选择性开发了一个分析模型，该模型取决于关键参数，例如表面拓扑，浆果力的大小和核摩擦。在这个动力学模型中，静态电子结构计算（在具有自旋轨道耦合（GHF+SOC）理论的广义Hartree-fock水平上）表明，电子自旋诱导的浆果力确实确实会导致甲氧基自由基异构化的明显变化。
We investigate how the Berry force (i.e. the pseudo-magnetic force operating on nuclei as induced by electronic degeneracy and spin-orbit coupling (SOC)) might modify a post-transition state bifurcation (PTSB) reaction path and affect product selectivity for situations when multiple products share the same transition state. To estimate the magnitude of this effect, Langevin dynamics are performed on a model system with a valley-ridge inflection (VRI) point in the presence of a magnetic field (that mimics the Berry curvature). We also develop an analytic model for such selectivity that depends on key parameters such as the surface topology, the magnitude of the Berry force, and the nuclear friction. Within this dynamical model, static electronic structure calculations (at the level of generalized Hartree-Fock with spin-orbit coupling (GHF+SOC) theory) suggest that electronic-spin induced Berry force effects may indeed lead to noticeable changes in methoxy radical isomerization.
