The accommodation of an excess electron by polycyclic aromatic hydrocarbons (PAHs) has important chemical and technological implications ranging from molecular electronics to charge balance in interstellar molecular clouds. Here, we use two-dimensional photoelectron spectroscopy and equation-of-motion coupled-cluster calculations of the radical anions of acridine (C13H9N-) and phenazine (C12H8N2-) and compare our results for these species to those for the anthracene anion (C14H10-). The calculations predict the observed resonances and additionally find low-energy two-particle-one-hole states, which are not immediately apparent in the spectra, and offer a slightly revised interpretation of the resonances in anthracene. The study of acridine and phenazine allows us to understand how N atom substitution affects electron accommodation. While the electron affinity associated with the ground state anion undergoes a sizable increase with the successive substitution of N atoms, the two lowest energy excited anion states are not affected significantly by the substitution. The net result is that there is an increase in the energy gap between the two lowest energy resonances and the bound ground electronic state of the radical anion from anthracene to acridine to phenazine. Based on an energy gap law for the rate of internal conversion, this increased gap makes ground state formation progressively less likely, as evidenced by the photoelectron spectra.

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This roadmap reviews the new, highly interdisciplinary research field studying the behavior of condensed matter systems exposed to radiation. The Review highlights several recent advances in the field and provides a roadmap for the development of the field over the next decade. Condensed matter systems exposed to radiation can be inorganic, organic, or biological, finite or infinite, composed of different molecular species or materials, exist in different phases, and operate under different thermodynamic conditions. Many of the key phenomena related to the behavior of irradiated systems are very similar and can be understood based on the same fundamental theoretical principles and computational approaches. The multiscale nature of such phenomena requires the quantitative description of the radiation-induced effects occurring at different spatial and temporal scales, ranging from the atomic to the macroscopic, and the interlinks between such descriptions. The multiscale nature of the effects and the similarity of their manifestation in systems of different origins necessarily bring together different disciplines, such as physics, chemistry, biology, materials science, nanoscience, and biomedical research, demonstrating the numerous interlinks and commonalities between them. This research field is highly relevant to many novel and emerging technologies and medical applications.

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We present a general two-dimensional model of conical intersection between metastable states that are vibronically coupled not only directly but also indirectly through a virtual electron in the autodetachment continuum. This model is used as a test ground for the design and comparison of iterative solvers for resonance dynamics in low-energy electron-molecule collisions. Two Krylov-subspace methods with various preconditioning schemes are compared. To demonstrate the applicability of the proposed methods on even larger models, we also test the performance of one of the methods on a recent model of vibrational excitation of CO2 by electron impact based on three vibronically coupled discrete states in continuum (Renner-Teller doublet of shape resonances coupled to a sigma virtual state) including four vibrational degrees of freedom. Two-dimensional electron energy-loss spectra resulting from electron-molecule scattering within the models are briefly discussed.

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Cyanogen NCCN and cyanoacetylene HCCCN are isoelectronic molecules, and as such, they have many similar properties. We focus on the bond cleavage in these induced by the dissociative electron attachment. In both molecules, resonant electron attachment produces CN- with very similar energy dependence. We investigate the very different dissociation dynamics, in each of the two molecules, revealed by velocity map imaging of this common fragment. Different dynamics are manifested both in the excess energy partitioning and in the angular distributions of fragments. Based on the comparison with electron energy loss spectra, which provide information about possible parent states of the resonances (both optically allowed and forbidden excited states of the neutral target), we ascribe the observed effect to the distortion of the nuclear frame during the formation of core-excited resonance in cyanoacetylene. The proposed mechanism also explains a puzzling difference in the magnitude of the CN- cross section in the two molecules which has been so far unexplained.

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