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Photoelectrons Are Not Always Quite Free.
J Phys Chem Lett ; 10(2): 144-149, 2019 Jan 17.
Artigo em Inglês | MEDLINE | ID: mdl-30569715
ABSTRACT
The photoelectron spectra of Sm2O- obtained over a range of photon energies exhibit anomalous changes in relative excited-state band intensities. Specifically, the excited-state transition intensities increase relative to the transition to the neutral ground state with decreasing photon energy, the opposite of what is expected from threshold effects. This phenomenon was previously observed in studies on several Sm-rich homo- and heterolanthanide oxides collected with two different harmonic outputs of a Nd:YAG (2.330 and 3.495 eV) [ J. Chem. Phys. 2017, 146, 194310]. We relate these anomalous intensities to populations of ground and excited anionic and neutrals states through the inspection of time-dependent perturbation theory within the adiabatic and sudden limits and for the first time show that transition intensities in photoelectron spectroscopy have a deep significance in gauging participation from excited states. We believe our results will have significance in the study of other electron-rich systems that have especially high density of accessible spin states.

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Texto completo: Disponível Coleções: Bases de dados internacionais Base de dados: MEDLINE Idioma: Inglês Revista: J Phys Chem Lett Ano de publicação: 2019 Tipo de documento: Artigo País de afiliação: Estados Unidos