Photochemical pathways in astronomical ices: A computational study of singlet oxygen reactions with hydrocarbons.

Complex organic molecules are widespread in different areas of the interstellar medium, including cold areas, such as molecular clouds, where chemical reactions occur in ice. Among the observed molecules are oxygen-bearing organic molecules, which are of high interest given their significant role in astrobiology. Despite the observed rich chemistry, the underlying molecular mechanisms responsible for molecular formation in such cold dilute areas are still not fully understood.

Symmetry-breaking dynamics of a photoionized carbon dioxide dimer.

Photoionization can initiate structural reorganization of molecular matter and drive formation of new chemical bonds. Here, we used time-resolved extreme ultraviolet (EUV) pump - EUV probe Coulomb explosion imaging of carbon dioxide dimer ion dynamics, that combined with ab initio molecular dynamics simulations, revealed unexpected asymmetric structural rearrangement. We show that ionization by the pump pulse induces rearrangement from the slipped-parallel (C) geometry of the neutral dimer towards a T-shaped (C) structure on the ~100 fs timescale, although the most stable slipped-parallel (C) structure of the ionic dimer.

An "inverse" harpoon mechanism.

Electron-transfer reactions are ubiquitous in chemistry and biology. The electrons' quantum nature allows their transfer across long distances. For example, in the well-known harpoon mechanism, electron transfer results in Coulombic attraction between initially neutral reactants, leading to a marked increase in the reaction rate.

Sequential and concerted C-C and C-O bond dissociation in the Coulomb explosion of 2-propanol.

We study the competing mechanisms involved in the Coulomb explosion of 2-propanol CH CHOH dication, formed by an ultrafast extreme ultraviolet pulse. Over 20 product channels are identified and characterized using 3D coincidence imaging of the ionic fragments. The momentum correlations in the three-body fragmentation channels provide evidence for a dominant sequential mechanism, starting with the cleavage of a C-C bond, ejecting CH and CHCHOH cations, followed by a secondary fragmentation of the hydroxyethyl cation that can be delayed for up to a microsecond after ionization.

Absence of Triplets in Single-Photon Double Ionization of Methanol.

Despite the abundance of data concerning single-photon double ionization of methanol, the spin state of the emitted electron pair has never been determined. Here we present the first evidence that identifies the emitted electron pair spin as overwhelmingly singlet when the dication forms in low-energy configurations. The experimental data show that while the yield of the CHO + H Coulomb explosion channel is abundant, the metastable methanol dication is largely absent.