An experimental and theoretical study of the C 1s ionization satellites in CH3I.

Abstract

The C 1s ionization spectrum of CH3I has been studied both experimentally and theoretically. Synchrotron radiation has been employed to record polarization dependent photoelectron spectra at a photon energy of 614 eV. These spectra encompass the main-line due to the C 1s single-hole state and the peaks associated with the shake-up satellites. Vertical ionization energies and relative photoelectron intensities have been computed using the fourth-order algebraic-diagrammatic construction approximation scheme for the one-particle Green's function and the 6-311++G** basis set. The theoretical spectrum derived from these calculations agrees qualitatively with the experimental results, thereby allowing the principal spectral features to be assigned. According to our calculations, two 2A1 shake-up states of the C 1s-1 σCI → σCI * type with singlet and triplet intermediate coupling of the electron spins (S' = 0, 1) play an important role in the spectrum and contribute significantly to the overall intensity. Both of these states are expected to have dissociative diabatic potential energy surfaces with respect to the C-I separation. Whereas the upper of these states perturbs the manifold of Rydberg states, the lower state forms a band which is characterized by a strongly increased width. Our results indicate that the lowest shake-up peak with significant spectral intensity is due to the pair (S' = 0, 1) of 2E (C 1s-1 I 5p → σCI *) states. We predict that these 2E states acquire photoelectron intensity due to spin-orbit interaction. Such interactions play an important role here due to the involvement of the I 5p orbitals.