No abstract

Theoretical and experimental study of vibrationally resolved partial photoionization cross sections and angular asymmetry parameter β for the 1σg and 1σu shells of N2 molecule in the region of the σ* shape resonance is reported. The measurements were made at the synchrotron radiation facility SPring-8 in Japan. The calculations in the random phase approximation have been performed using the relaxed core Hartree–Fock wavefunctions with the fractional charge of the ion core equal to 0.7. With its help, the role of interchannel coupling between the closely spaced 1σg and 1σu shells was studied. The experiment demonstrates the existence of a correlational maximum in the 1σu shell photoionization cross section induced by the σ* shape resonance in the 1σg shell. This maximum reveals itself even more clearly in the angular asymmetry parameter β for the v′ = 0 and v′ = 1 vibrational states of the ion. The calculation in the random phase approximation gives a consistent interpretation of the experimental data.

The ratios of photoionization cross sections of the 1σg and 1σu shells of the N2 molecule for the vibrational transitions to the v′ = 0 and v′ = 1 core-ionized states in the photon energy region between 440 and 550 eV have been measured. The calculations in the random phase approximation well reproduce the experimental data. The variation of the ratio with photon energy is attributed to the interference modulation that is caused by coherent photoemission from the two atoms, as an analogue of the Young's double-slit experiment. The calculations extended up to 1.8 keV allow connecting the modulation with the onset of transitions to the states of increasing orbital angular momentum which occurs at increasing photon energies and demonstrate that the main contribution to these modulations comes from the σ continuum states.

We have measured the vibrational structures of the N 1s photoelectron mainline and satellites of the gaseous N2 molecule with the resolution better than 75 meV. The gerade and ungerade symmetries of the core-ionized (mainline) states are resolved energetically, and symmetry-dependent angular distributions for the satellite emission allow us to resolve the Sigma and Pi symmetries of the shake-up (satellite) states. Symmetry-adapted cluster-expansion configuration-interaction calculations of the potential energy curves for the mainline and satellite states along with a Franck-Condon analysis well reproduce the observed vibrational excitation of the bands, illustrating that the theoretical calculations well predict the symmetry-dependent geometry relaxation effects. The energies of both mainline states and satellite states, as well as the splitting between the mainline gerade and ungerade states, are also well reproduced by the calculation: the splitting between the satellite gerade and ungerade states is calculated to be smaller than the experimental detection limit.

No abstract