Photon-energy-programmable subnanometric electron birth-site control

Optical control of electron-generation sites has broadly enabled ultrafast nanoscale imaging, spectroscopy, and functional control. Existing approaches achieve nanoscale site selectivity by shaping localised optical fields around nanostructures, thereby limiting independent site selectivity within the same local-field hotspot. Here, using a single-molecule electron emitter, we show that site selectivity can instead be encoded in the electronic excitation pathway, enabling subnanometric control of electron birth sites within the same local-field hotspot. By tuning the photon energy, we selectively access molecular states of different spatial symmetry and reversibly switch the electron birth site between distinct locations in the same emitter, with the change read out directly in the far-field emission pattern. The switching depends on photon energy alone and is absent under variations in intensity or polarisation. Our results establish optical birth-site selectivity that is not dictated by the local-field distribution, opening a route to electron birth-site control through the electronic excitation pathway.