Spectroscopy of temporary anion states: Renner–Teller coupling and electronic autodetachment in copper difluoride anion

Abstract

Internal level structures of temporary anion states (resonances) are probed using action spectroscopy obtained from photoelectron imaging of CuF2−.

Low energy electron impact resonances of anthracene probed by 2D photoelectron imaging of its radical anion

“…Modulation between direct and indirect detachment as a function of hv have been noted in the photoelectron spectra of other anionic molecules. For example, Mabbs and coworkers observed changes in cross section in the PE spectra of CuF2 -, 58 and Chick-Jarrold and coworkers recently noted interesting oscillations in the PE spectra of Sm2O -. 59 We have also previously seen such oscillation for larger organic compounds and clusters.…”

Photoelectron Spectra of Gd2O2− and Non-Monotonic Photon-Energy Dependent Variations in Populations of Close-Lying Neutral States

“…8 The reasonable agreement between DFT, LFT and experiment provides a measure of validation for the DFT calculations in predicting the energy ordering of the states. As shown in Figure 3, the highest spin anion 16 B1u is predicted to be the lowest energy state, with the AFM-coupled analog, 2 B1u, state lying 0.07 eV higher. The small energy difference calls into question the identity of the true ground state.…”

“…The states indicated by green boxes are connected by one-electron loss of the anion. AFM 3 B1u analog, and similarly, the FM-coupled 16 B1u state is predicted to be lower in energy than its AFM 2 B1u analog, which suggests that unpaired outer-valence electrons stabilize FM coupling between the 4f 7 cores. We note that the AFM-coupled analog to the open shell 15-tet states, the 1 B1u state, is also calculated to be very close in energy to these three 15 B1u states.…”

“…Resonance with excited anion states embedded in the detachment continuum can have pronounced effects on the intensities of detachment transitions, with a few examples included in the references. [13][14][15][16][17][18] However, the underlying source of the changes in excited state intensities in the case of these samarium-containing suboxide clusters appeared to be shake-up transitions or internal inelastic scattering from strong photoelectron-valence electron (PEVE) interactions. To explore this effect in more detail, we demonstrated an increase in the relative intensity of an unresolved manifold of excited state transitions in the Sm2O − PE spectrum that was inversely proportional to the momentum of the photoelectrons by measuring the spectrum over a range of photon energies.…”

Elektronische Resonanzzustände – warum die Energie komplex sein kann, Trendbericht Theoretische Chemie 2020, Teil 1

“…44) Jüngste Anwendungen nichthermitescher Methoden umfassen die Untersuchung von Elektronenanlagerung an den astrochemisch relevanten Kohlenstoffverbindungen C x N (x=1, 3, 5, 7) 45) sowie an DNA-Basen 46) mit CAP-EOM-CC-Metho-den. Außerdem wurden Photodetachmentspektren 47) und Elektronenenergieverlustspektren 36,37) sowie DEA an Peptidbindungen 48) und Chlorethylene 34,37) mit CAP-Methoden untersucht.…”