Coherent atomic orbital polarization probes the geometric phase in photodissociation of polyatomic molecules
Coherent atomic orbital polarization probes the geometric phase in photodissociation of polyatomic molecules
复制标题
相干原子轨道偏振探测多原子分子光解离的几何相位
DOI：
10.1002/ntls.20220013
复制
发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Vasyutinskii, Oleg S.
中科院分区：
文献类型：
--
作者：
Weeraratna, Chaya;Suits, Arthur G.;Vasyutinskii, Oleg S.
分子光解过程中多种途径之间的量子干涉通常会导致原子产物的角动量极化，这可以深入了解基本物理过程。对于双原子分子的解离，所产生的轨道极化是完全理解的，并且符合量子力学理论。然而，对于多原子分子，相干光碎片轨道极化经常被观察到，但迄今为止还没有得到理论解释，并且缺乏物理洞察力。在这里，我们提出了一个臭氧光解作用的模型，揭示了几何相的新表现形式的重要性。我们证明，这种几何相位效应允许相干偏振在某些情况下存在，否则它会消失，并在某些情况下抵消它，否则它可能存在。该模型解释了迄今为止无法解释的臭氧测量结果，并代表了对多原子分子中相干电子激发和几何相位的新作用的更深入理解的一步。相干光碎片原子轨道偏振揭示了物质波在多路径解离过程中的干扰。在双原子分子中，这是很好的理解，但在多原子分子中，可以看到很大的影响，但这些都没有严格的解释。建立了一个模型，描述了臭氧紫外解离中的这些现象，该模型解释了许多相互矛盾的观察结果，并揭示了分子物理中几何相的新表现形式。
Quantum interference between multiple pathways in molecular photodissociation often results in angular momentum polarization of atomic products and this can give deep insight into fundamental physical processes. For dissociation of diatomic molecules, the resulting orbital polarization is fully understood and consistent with quantum mechanical theory. For polyatomic molecules, however, coherent photofragment orbital polarization is frequently observed but so far has eluded theoretical explanation, and physical insight is lacking. Here, we present a model of these effects for ozone photodissociation that reveals the importance of a novel manifestation of the geometric phase. We show this geometric phase effect permits the existence of coherent polarization in cases where it would otherwise vanish, and cancels it in some cases where it might otherwise exist. The model accounts for measurements in ozone that have hitherto defied explanation, and represents a step toward a deeper understanding of coherent electronic excitation in polyatomic molecules and a new role of the geometric phase.Key PointsCoherent photofragment atomic orbital polarization reveals matter wave interference in dissociation along multiple paths.In diatomic molecules, this is well‐understood, but in polyatomic molecules, large effects are seen but these have defied a rigorous explanation.A model is developed describing these phenomena in the UV dissociation of ozone that accounts for a number of conflicting observations and reveals a new manifestation of the geometric phase in molecular physics.