Imaging the Breakdown of Molecular-Frame Dynamics through Rotational Uncoupling

Abstract

We demonstrate the breakdown of molecular-frame dynamics induced by the uncoupling of molecular rotation from electronic motion in molecular Rydberg states. We observe this non-Born-Oppenheimer regime in the time domain through photoelectron imaging of a coherent molecular Rydberg wave packet in ${\text{N}}_2$. The photoelectron angular distribution shows a radically different time evolution than that of a typical molecular-frame-fixed electron orbital, revealing the uncoupled motion of the electron as it precesses around the $averaged$ anisotropic potential of the rotating ion-core.

6 pages, 4 figures

References in corpus (2)

• Photoelectron angular distributions from strong-field ionization of oriented molecules
• Adiabatic field-free alignment of asymmetric top molecules with an optical centrifuge