Low-Energy Nondipole Effects in Molecular Nitrogen Valence-Shell Photoionization

Observations are reported for the first time of significant nondipole effects in the photoionization of the outer-valence orbitals of diatomic molecules. Measured nondipole angular-distribution parameters for the 3σ_g, 1π_u, and 2σ_u shells of N₂ exhibit spectral variations with incident photon energies from thresholds to ∼200  eV which are attributed via concomitant calculations to particular final-state symmetry waves arising from (E1)⊗(M1,E2) radiation-matter interactions first-order in photon momentum. Comparisons with previously reported K-edge studies in N₂ verify linear scaling with photon momentum, accounting in part for the significantly enhanced nondipole behavior observed in inner-shell ionization at correspondingly higher momentum values in this molecule.