We observe photochemical selectivity for N 1s to pi(*) excitations of chemisorbed N2. By narrow bandwidth synchrotron radiation we selectively excite one of the two atoms of the molecule. Photon stimulated desorption of neutral N atoms predominates for excitations of the N atom close to the surface, whereas excitation of the outer atom ejects predominantly N02 and small amounts of N+, demonstrating the predominant breaking of the inner or outer bond, respectively, of the N2 adsorbate. Analysis on the basis of previously obtained decay electron spectra after atom-selective excitation can explain the mechanism of localized bond breaking.
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