The time scale for electronic reorganization upon sudden ionization of the water and water-methanol hydrogen bonded dimers and of the weakly bound NO dimer

Abstract

When the valence molecular orbital is localized sudden ionization can cause the nascent hole to move rapidly even before any relaxation of the geometry occurs. Hydrogen bonded clusters offer suitable test systems where the hole is initially localized on one moiety. Computational studies are reported for the water dimer and water-methanol bimer. The local ionization potential of water is different in the methanol-water and water-methanol conformers and this difference is very clearly reflected in the dynamics of charge migration. For the NO dimer the results are that its structure is symmetric so that the two NO molecules are equivalent and do not exhibit the required localization. The role of symmetry is also evident in the charge propagation for holes created in different orbitals. Localization of the initial hole distribution even if absent in the bare molecule can still be induced by the intense electric field of a sudden photoionization. This effect is computationally studied for the NO dimer in the presence of a static electric field.