Intra-configuration fine-structure transitions in highly charged ions (HCIs) result in most cases from changes in the coupling of equivalent electrons. They are multipole forbidden to varying degrees and often occur within the optical range. In HCI with semi-filled $n{\mathrm{d}}^{}$ and $n{\mathrm{f}}^{}$ subshells, electrons can in principle couple to states which are energetically close but with very different total angular momenta, e.g. $\mathrm{0\le J\le 10}$. This gives rise to metastable states with very long lifetimes that exhibit particularly interesting clock transitions or, as in the case of orbital level crossings, acquire a considerable sensitivity to a possible variation of the fine-structure constant α. We investigate both experimentally and theoretically connecting the ground state and adjacent states of Pb XXII to Pb XXXIV and Bi X to Bi XV, respectively, covering complex couplings of electrons in the $4{\mathrm{f}}^{}$ and $5{\mathrm{d}}^{}$ shells. These and others such as $n{\mathrm{d}}^{}$ and $n{\mathrm{f}}^{}$, which also contain equivalent electrons, are of interest for frequency metrology using quantum logic spectroscopy, for atomic structure and QED theory tests, and for the search for Dark Matter candidates. We infer their level structure, benchmark calculations from two different electronic structure codes, and lay the groundwork for inferring the wavelengths of forbidden transitions of higher multipolarity in the optical and VUV region.

Nanoparticles devoted to improve radiotherapy treatments are an efficient tool if they can induce the formation of deleterious species in the tumor. Their interaction with radiation is responsible for radical production but in spite of the numerous studies mostly with cells, no consensus has been reached about radical formation mechanism. In order to gain knowledge in the physico-chemical step of this phenomenon, we applied a very sensitive test to quantify hydroxyl radicals and electrons produced when gold atoms, organized as nanoparticles or as a salt in solution, are irradiated by keV and MeV photons (x- and γ- rays). The crucial role of interfacial water is suggested to explain the high quantity of radicals measured for nanoparticles. These experimental data were supplemented by classical molecular dynamics simulations, revealing a specific organization of the water hydrogen bonding network at the nanoparticle surface which could be a key component in the mechanism of radical production by irradiated colloidal suspensions.

We have simulated two mechanisms, direct and superexchange, for the electron transfer in a model Bis(hydrazine) Radical Cation, which consists of two hydrazine moieties coupled by a benzene ring. The computations, that are inspired by the attochemistry approach, focus on the electron dynamics arising from a coherent superposition of four cationic states. The electron dynamics, originating from a solution of the time dependent Schrödinger equation within the Ehrenfest method, is coupled to the relaxation of the nuclei. Both direct (ca. 15 fs dynamics) and superexchange (ca. 2 fs dynamics) mechanisms are observed and turn out to lie on a continuum depending on the strength of the coupling of the benzene bridge electron dynamics with the hydrazine chromophore dynamics. This contrasts with the chemical pathway approach where the direct mechanism is completely non-adiabatic via a conical intersection, while the superexchange mechanism involves an intermediate radical with the unpaired electron localized on the benzene ring. Thus, with the attochemistry-inspired electron dynamics approach, one can distinguish direct from superexchange mechanisms depending on the strength of the coupling of two types of electron dynamics: the slow hydrazine dynamics (ca. 15 fs) and the fast benzene linker dynamics (ca. 2 fs). In this model bis(hydrazine) radical cation, only when the intermediate coupler is in an anti-quinoid state, does one see the coupling of the bridge and hydrazine chromophore dynamics.

Inter-particle Coulombic electron capture (ICEC) is an environment-enabled electron capture process by means of which a free electron can be efficiently attached to a system (e.g. ion, atom, molecule, or quantum dot (QD)). The excess electron attachment energy is simultaneously transferred to a neighbouring system which concomitantly undergoes ionization (or excitation). ICEC has been theoretically predicted in van-der-Waals and in hydrogen-bonded systems as well as in QD arrays. The theoretical approaches employed in these works range from analytical models to electronic structure and (quantum) dynamical calculations. In this article, we provide a comprehensive review of the main theoretical approaches that have been developed and employed to investigate ICEC and summarize the main conclusions learned from these works. Since knowledge on ICEC is still in its early stage, we conclude this review with our own views and proposals on the future perspectives for the research in ICEC.

We employ the Markov approximation and the well-known Fresnel-integral to derive in 'one-line' the familiar expression for the Landau–Zener transition probability. Moreover, we provide numerical as well as analytical justifications for our approach, and identify three characteristic motions of the probability amplitude in the complex plane.