Precise control and study of molecules is challenging due to the variety of internal degrees of freedom and local coordinates that are typically not controlled in an experiment. Employing quantum gas microscopy to position and resolve the atoms in Rydberg macrodimer states solves most of these challenges and enables unique access to the molecular frame. Here, we demonstrate this approach and present photoassociation studies in which the molecular orientation relative to an applied magnetic field, the polarization of the excitation light, and the initial atomic state are fully controlled. The observed dependencies allow for an electronic structure tomography of the molecular state. We additionally observe an orientation-dependent Zeeman shift, and we reveal a significant influence on it caused by the hyperfine interaction of the macrodimer state. Finally, we demonstrate control over the electrostatic binding potential by engineering a gap between two crossing pair potentials. Our results establish macrodimers as the most sensitive tool to benchmark Rydberg interaction potentials, and they open new perspectives for improving Rydberg dressing schemes.

• Received 5 October 2020
• Revised 11 January 2021
• Accepted 18 February 2021

DOI:https://doi.org/10.1103/PhysRevResearch.3.013252

Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI. Open access publication funded by the Max Planck Society.

Published by the American Physical Society