Covalent bonds in positron dihalides.

We report a computational study on homo- and heteronuclear e+[X-Y-] compounds formed by two halide anions (X-, Y- = F-, Cl-, Br-) and one positron. Our results indicate the formation of energetically stable positronic molecules in all cases. Analysis of the electron and positron densities points out that the formation of positron covalent bonds underlies the stabilization of the otherwise repelling dihalides, revealing that positronic bonding can reach far beyond the previously addressed e+[H-H-] molecule [J. Charry, M. T. do N. Varella and A. Reyes, Angew. Chem. Int. Ed., 2018, 57, 8859-8864.]. To a significant extent, the properties of the positron dihalides are similar to those of the purely electronic analogs, e-[A+B+], molecular cations with isoelectronic atomic cores (A+, B+ = Na+, K+, Rb+) bound by one electron. The positron bonds in the e+[X-Y-] complexes are however stronger than those in the isoelectronic e-[A+B+] counterparts, as the former have shorter bond lengths and higher bond energies. While an energy decomposition analysis points out that both electronic and positronic bonds essentially arise from electrostatic interactions, the more stable positron bonds are partly due to the higher polarizabilities of the dihalide anions, and partly to more significant contributions from correlation and relaxation effects.

Electron-Induced Reactions in 3-Bromopyruvic Acid.

3-Bromopyruvic acid (3BP) is a potential anti-cancer drug, the action of which on cellular metabolism is not yet entirely clear. The presence of a bromine atom suggests that it is also reactive towards low-energy electrons, which are produced in large quantities during tumour radiation therapy. Detailed knowledge of the interaction of 3BP with secondary electrons is a prerequisite to gain a complete picture of the effects of 3BP in different forms of cancer therapy. Herein, dissociative electron attachment (DEA) to 3BP in the gas phase has been studied both experimentally by using a crossed-beam setup and theoretically through scattering and quantum chemical calculations. These results are complemented by a vacuum ultraviolet absorption spectrum. The main fragmentation channel is the formation of Br- close to 0 eV and within several resonant features at 1.9 and 3-8 eV. At low electron energies, Br- formation proceeds through σ* and π* shape resonances, and at higher energies through core-excited resonances. It is found that the electron-capture cross-section is clearly increased compared with that of non-brominated pyruvic acid, but, at the same time, fragmentation reactions through DEA are significantly altered as well. The 3BP transient negative ion is subject to a lower number of fragmentation reactions than those of pyruvic acid, which indicates that 3BP could indeed act by modifying the electron-transport chains within oxidative phosphorylation. It could also act as a radio-sensitiser.

The electron-furfural scattering dynamics for 63 energetically open electronic states.

We report on integral-, momentum transfer- and differential cross sections for elastic and electronically inelastic electron collisions with furfural (C5H4O2). The calculations were performed with two different theoretical methodologies, the Schwinger multichannel method with pseudopotentials (SMCPP) and the independent atom method with screening corrected additivity rule (IAM-SCAR) that now incorporates a further interference (I) term. The SMCPP with N energetically open electronic states (N(open)) at either the static-exchange (N(open) ch-SE) or the static-exchange-plus-polarisation (N(open) ch-SEP) approximation was employed to calculate the scattering amplitudes at impact energies lying between 5 eV and 50 eV, using a channel coupling scheme that ranges from the 1ch-SEP up to the 63ch-SE level of approximation depending on the energy considered. For elastic scattering, we found very good overall agreement at higher energies among our SMCPP cross sections, our IAM-SCAR+I cross sections and the experimental data for furan (a molecule that differs from furfural only by the substitution of a hydrogen atom in furan with an aldehyde functional group). This is a good indication that our elastic cross sections are converged with respect to the multichannel coupling effect for most of the investigated intermediate energies. However, although the present application represents the most sophisticated calculation performed with the SMCPP method thus far, the inelastic cross sections, even for the low lying energy states, are still not completely converged for intermediate and higher energies. We discuss possible reasons leading to this discrepancy and point out what further steps need to be undertaken in order to improve the agreement between the calculated and measured cross sections.

Real-time observation of intramolecular proton transfer in the electronic ground state of chloromalonaldehyde: an ab initio study of time-resolved photoelectron spectra.

The authors report on studies of time-resolved photoelectron spectra of intramolecular proton transfer in the ground state of chloromalonaldehyde, employing ab initio photoionization matrix elements and effective potential surfaces of reduced dimensionality, wherein the couplings of proton motion to the other molecular vibrational modes are embedded by averaging over classical trajectories. In the simulations, population is transferred from the vibrational ground state to vibrationally hot wave packets by pumping to an excited electronic state and dumping with a time-delayed pulse. These pump-dump-probe simulations demonstrate that the time-resolved photoelectron spectra track proton transfer in the electronic ground state well and, furthermore, that the geometry dependence of the matrix elements enhances the tracking compared with signals obtained with the Condon approximation. Photoelectron kinetic energy distributions arising from wave packets localized in different basins are also distinguishable and could be understood, as expected, on the basis of the strength of the optical couplings in different regions of the ground state potential surface and the Franck-Condon overlaps of the ground state wave packets with the vibrational eigenstates of the ion potential surface.