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 almost all of these challenges and enables unique access to the molecular frame. Here, we demonstrate the power of this approach and present first photoassociation studies for different molecular symmetries 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 characteristic dependencies allow for an electronic structure tomography of the molecular state. We additionally observe an orientation-dependent Zeeman shift and reveal a significant influence on it caused by the hyperfine interaction of the macrodimer state. Finally, we demonstrate controlled engineering of the electrostatic binding potential by opening a gap in the energetic vicinity of two crossing pair potentials.
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