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- W2000433266 abstract "Predissociation of superexcited states of OCS is studied by two-dimensional photoelectron spectroscopy using synchrotron radiation in the photon energy range of 15–16.5 eV. A two-dimensional photoelectron spectrum exhibits two kinds of characteristic patterns both of which are ascribed to autoionization of sulfur atoms. This superexcited atom S* is produced by predissociation of a Rydberg state OCS*(RB) converging to OCS+(B̃ 2Σ+). The pattern of the first kind results from predissociation processes in which the effective principal quantum number n of the Rydberg electron is almost conserved. This suggests that the Rydberg electron behaves as a spectator because of its negligibly weak interaction with the ion core (spectator predissociation). On the contrary, n of S* does not accord with that of OCS*(RB) in the pattern of the second kind, indicating that the Rydberg electron participates directly in the electron exchange mechanism controlling conversion from OCS*(RB) to a predissociating state (participant predissociation). With increasing n, OCS*(RB) decays more preferentially by the spectator than by the participant predissociation. The spectator predissociation of OCS*(RB) proceeds through a two-step conversion which involves Rydberg states converging to OCS+(Ã 2Π and X̃ 2Π) and a dissociative multiple-electron-excited satellite state OCS* (SAT) asymptotically correlating with S*+CO(X̃ 1Σ+). In contrast, the participant predissociation may be accounted for by a direct conversion from OCS*(RB) to OCS*(SAT). The quantum yields are estimated to be 0.06 and 0.02 for the spectator and participant predissociation, respectively, at the incident photon energy of 15.95 eV where OCS*(RB) states with n∼12 lie. A simulation is performed to reproduce the partial cross section curve for the spectator predissociation by using a model in which the decay rates for the participant and spectator predissociation are assumed to be proportional to n−3 and n0, respectively. The simulated and experimental cross section curves are in good agreement with each other in the photon energy range of 15.8–16.04 eV." @default.
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- W2000433266 date "1999-01-01" @default.
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- W2000433266 title "Spectator- and participant-like behavior of a Rydberg electron on predissociation of superexcited states of OCS" @default.
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- W2000433266 doi "https://doi.org/10.1063/1.478068" @default.
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