Abstract

The Auger electron photoion coincidence (AEPICO) technique has been applied for the study of H+ desorption induced by resonant excitations of O 1s of condensed H2O. The peak positions of the AEPICO yield spectrum at the 4a1←O 1s resonance (hν=533.4 eV) are found to correspond to spectator-Auger transitions leaving (O 2s)−2(4a1)1, (O 2s)−1(O 2p)−1(4a1)1, and (O 2p)−2(4a1)1 states. The H+ AEPICO yield is greatly enhanced at 4a1←O 1s while it is suppressed at 3p←O 1s (hν=537 eV) as compared with that at the O 1s ionization (hν=560 eV). On the basis of these results, the ultrafast ion desorption mechanism is suggested to be favorable for the H+ desorption at 4a1←O 1s, that is, the repulsive potential energy surface of the (O 1s)−1(4a1)1 state is responsible for the H+ desorption. For H+ desorption at 3p←O 1s, a spectator-Auger stimulated ion desorption mechanism is concluded to be probable. The suppression of the H+ AEPICO yield is ascribed to the reduction of the hole–hole repulsion due to the shield effect of the 3p electron. These results demonstrate the power of the AEPICO technique to clarify the mechanism of ion desorption induced by core–electron excitations.

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