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Zusammenfassung:
Manifestations of the condensed phase dimer formation on the N 1s and O 1s core-hole shake-up structure of nitrobenzene are examined theoretically within the CNDO/S CI equivalent-core approximation. Computations on the nitrosobenzene dimer (diazobenzene dioxide) were performed to simulate the solid state environment. Results obtained using singly excited and singly and doubly excited ("singlet"-coupled) configurations are contrasted to emphasize the importance of correlation contributions. Although intermolecular interactions are found to strongly determine the nature of the solid state spectra, the final state energy and intensity distributions are similar for the vapor (monomer) and condensed phase (dimer) systems as observed experimentally. This "accidental" correspondence is discussed in terms of component contributions to the spectral functions. Computations on the N 1s and O 1s hole states of the nitric oxide (NO) dimer yield results in close agreement with existing condensed phase spectra of NO. Various similarities between the core-hole induced "intermolecular" interactions in the nitrosobenzene dimer and nitric oxide dimer systems are noted and discussed. Finally, comparison of the UPS spectrum of condensed phase nitric oxide with appropriate valence level calculation on the dimer also indicates strong hole-induced "intermolecular" effects consistent with the analysis of the core-level region.
