Heck Saijoscha, Baykusheva Denitsa, Han Meng, Ji Jia-Bao, Perry Conaill, Gong Xiaochun, Wörner Hans Jakob
Laboratorium für Physikalische Chemie, ETH Zürich, 8093 Zürich, Switzerland.
Department of Physics, Harvard University, Cambridge, MA 02138, USA.
Sci Adv. 2021 Dec 3;7(49):eabj8121. doi: 10.1126/sciadv.abj8121.
Shape resonances play a central role in many areas of science, but the real-time measurement of the associated many-body dynamics remains challenging. Here, we present measurements of recoil frame angle-resolved photoionization delays in the vicinity of shape resonances of CF. This technique provides insights into the spatiotemporal photoionization dynamics of molecular shape resonances. We find delays of up to ∼600 as in the ionization out of the highest occupied molecular orbital (HOMO) with a strong dependence on the emission direction and a pronounced asymmetry along the dissociation axis. Comparison with quantum-scattering calculations traces the asymmetries to the interference of a small subset of partial waves at low kinetic energies and, additionally, to the interference of two overlapping shape resonances in the HOMO-1 channel. Our experimental and theoretical results establish a broadly applicable approach to space- and time-resolved photoionization dynamics in the molecular frame.
形状共振在许多科学领域中都起着核心作用，但对相关多体动力学进行实时测量仍然具有挑战性。在此，我们展示了对CF形状共振附近反冲框架角分辨光电离延迟的测量。该技术为分子形状共振的时空光电离动力学提供了见解。我们发现在从最高占据分子轨道（HOMO）电离时，延迟高达约600阿秒，强烈依赖于发射方向，并且沿解离轴具有明显的不对称性。与量子散射计算的比较将这种不对称性追溯到低动能下一小部分分波的干涉，此外，还追溯到HOMO - 1通道中两个重叠形状共振的干涉。我们的实验和理论结果建立了一种广泛适用的方法，用于研究分子框架中的空间和时间分辨光电离动力学。
