Changes in site-specific shape resonances in nitrogen K-shell photoionization of N₂O induced by vibrational excitation

The central (N_c) and terminal (N_t) nitrogen K-shell photoelectron spectra (PESs) of N₂O molecules have been measured in the σ shape resonance energy region at temperatures of ∼300 and ∼630 K. Estimating vibrational populations based on the Boltzmann distribution at these temperatures, PESs of vibrationally ground and bending-excited levels in the initial electronic ground state were extracted. Vibrationally integrated partial cross sections and asymmetry parameters for ionization from vibrationally ground and bending-excited levels were obtained as a function of the incident photon energy by integrating PESs over the vibrational levels of the core-hole states. In N_c photoionization, the shape resonance from the bending-excited level was found to be shifted to the lower photon energy side and to become narrower than that from the ground vibrational level. In N_t photoionization from the bending-excited level, the downward shift of the resonance is more significant than that in N_c ionization. These experimental findings are qualitatively consistent with theoretical predictions and suggest that the shape resonance associated with the N_t core hole is more sensitive to the bending angle of the initial state than is the shape resonance associated with the N_c core hole. The asymmetry parameters for photoionization from the bending-excited level, however, showed almost the same behavior as those from the ground vibrational level for both K-shell photoionization channels and in the photon energy range studied here.