The photoelectron spectra of Samarium-rich lanthanide oxides− 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 transition to the neutral ground state with decreasing photon energy, opposite of what is expected from Wigner threshold law. We relate these anomalous intensities to populations of ground and excited anionic and neutral states through 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. If time permits we will also discuss a new approach to treat these problems that includes explicit wavepacket dynamics of the electronic structure with the correct outgoing-wave boundary conditions programmed to study the photo-dissociation problem.

Adiabatic, sudden, and non-adiabatic processes in photoelectron spectroscopies involving samarium rich homo- and hetero-lanthanide oxides

2019 Spring National Meeting

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