Site-and state-selective dissociation of methyl acetate induced by core level excitation has been studied in the oxygen K-edge region using time-of-flight fragment-mass spectroscopy. O1s core (C=O/OMe) to valence (C{OMe ) excitation bands in the total-ion-yields of methyl acetate were assigned based on the comparison with those of other esters and band-deconvolution analysis. Product branching ratios of CD 3 þ and CDO þ cations from deuterium-labeled methyl-d 3 acetate (CH 3 C(O)OCD 3 ) showed that site-selective bond scission takes place between the (O1s CO À1 Ã CO ) and (O1s OMe À1 Ã CO ) sites, indicating the dissociation with an antibonding nature after the spectator Auger transitions. Although the efficient production of CDO þ was observed at the (O1s OMe À1 Ã C{OMe ) transition, however, no apparent state-selective dissociation of CD 3 þ could be observed at the (O1s OMe À1 Ã O{Me ). The present results indicate that the lack of state-selectivity at the (O1s OMe À1 Ã O{Me ) is largely due to the weak band intensity buried into the congestion of core-to-Rydberg transitions.
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