Fast Track Communication

Abstract Photoionization of Mg 3s is studied near the Cooper minimum in dipole channels using the relativistic-random-phase approximation. While the importance of first-order nondipole effects on photoelectron angular distributions at low energies is well known, it is reported here for the first time that in the energy region near the dipole Cooper minimum, quadrupole transitions are not just important, but actually dominate the total photoionization cross section. Studies of dipole-dipole, dipole-quadrupole and quadrupole-quadrupole interference terms in the photoelectron angular distribution show that in the region of dipole Cooper minimum even the calculation of the dipole angular distribution parameter, β, requires the inclusion of quadrupole channels. The significance of second-order [O(k 2 r 2 )] nondipole terms, primarily due to the contributions from electric quadrupole-quadrupole interference terms at photon energy as low as ∼11 eV, are shown to induce dramatic changes in the photoelectron angular distribution over a small energy range

A theoretical study on the formation of iodine oxide aggregates and monohydrates

Biotic and abiotic emissions of molecular iodine and iodocarbons from the sea or the ice surface and the intertidal zone to the coastal/polar marine boundary layer lead to the formation of iodine oxides, which subsequently nucleate forming iodine oxide particles (IOPs). Although the link between coastal iodine emissions and ultrafine aerosol bursts is well established, the details of the nucleation mechanism have not yet been elucidated. In this paper, results of a theoretical study of a range of potentially relevant aggregation reactions of different iodine oxides, as well as complexation with water molecules, are reported. Thermochemical properties of these reactions are obtained from high level ab initio correlated calculations including spin-orbit corrections. The results show that the nucleation path most likely proceeds through dimerisation of I2O4. It is also shown that water can hinder gas-to-particle conversion to some extent, although complexation with key iodine oxides does not remove enough of these to stop IOP formation. A consistent picture of this process emerges from the theoretical study presented here and the findings of a new laboratory study reported in the accompanying paper (Gomez Martin et al., 2013)