Microwave of known amplitude and frequency, irradiating the junction of a low temperature scanning tunneling microscope, was found to induce a dc signal. This rectification current is spatially localized and exhibits chemical sensitivity at the atomic scale. Dependence of the rectification current on the sample bias voltage reveals spin splitting in the electronic state of a single Mn atom and vibrations of single MnCO molecule. These results demonstrate the feasibility of atomic scale nonlinear spectroscopy and the potential for the detection of resonance phenomena excited with a spatially extended electromagnetic wave.
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