Can Anti-Aufbau DFT Calculations Estimate Singlet Excited State Aromaticity? Correspondence on “Dibenzoarsepins: Planarization of 8π-Electron System in the Lowest Singlet Excited State”

The simple anti-aufbau DFT approach for estimating singlet excited state aromaticity suggested in a recent Communication published in this journal is shown to produce incorrect results because it targets a linear combination of the singlet and triplet configurations involving the HOMO and LUMO rather than the first singlet excited state. If the S₁ state of a molecule is dominated by the HOMO→LUMO excitation, a comparably simple but theoretically consistent and qualitatively correct approximation to the S₁ wavefunction can be achieved by performing a small “two electrons in two orbitals” CASSCF(2,2) calculation which can be followed by the evaluation of magnetic aromaticity criteria such as NICS.     

Reconciling Electrostatic and n→π* Orbital Contributions in Carbonyl Interactions

Interactions between carbonyl groups are prevalent in protein structures. Earlier investigations identified dominant electrostatic dipolar interactions, while others implicated lone pair n→π* orbital delocalisation. Here these observations are reconciled. A combined experimental and computational approach confirmed the dominance of electrostatic interactions in a new series of synthetic molecular balances, while also highlighting the distance-dependent observation of inductive polarisation manifested by n→π* orbital delocalisation. Computational fiSAPT energy decomposition and natural bonding orbital analyses correlated with experimental data to reveal the contexts in which short-range inductive polarisation augment electrostatic dipolar interactions. Thus, we provide a framework for reconciling the context dependency of the dominance of electrostatic interactions and the occurrence of n→π* orbital delocalisation in C=O⋅⋅⋅C=O interactions.     

HILITE—A tool to investigate interactions of matter and light

Detailed investigations of laser–ion interactions require well-defined ion targets and detection techniques for high-sensitivity measurements of reaction educts and products. To this end, we have designed and built the High-Intensity Laser-Ion Trap Experiment Penning trap setup, which features various ion-target preparation techniques including selection, cooling, compression, and positioning as well as destructive and non-destructive measurement techniques to determine the number of stored ions for all charge states individually and simultaneously. We have recently performed first commissioning experiments of ion deceleration and dynamic ion capture with highly charged ion bunches from an electron beam ion source. We have characterized our single-pass non-destructive ion counter in detail and were able to determine the ion velocity as well as the number of ions from the signals acquired.     

Conditions for the Occurrence of Spontaneous Oscillating Magnetic Relaxation in Synthetic Pt/Co/Ir/Co/Pt Ferrimagnets

Physics of the Solid State - It has been established that nonmonotonic magnetization relaxation in Pt/Co/Ir/Co/Pt synthetic ferrimagnets (SF) with perpendicular magnetic anisotropy is caused by the...     

Propagation of Low-Energy Electrons and the Density of Unoccupied States in Ultrathin TCNQ Layers on the Oxidized Silicon Surface

Physics of the Solid State - The formation of unoccupied electronic states and the boundary potential barrier during thermal deposition of tetracyanoquinodimethane (TCNQ) films to 7 nm in thickness...     

Photocatalytic Systems Based on Acridine Salts Derivatives

Russian Journal of General Chemistry - The possibility of 10-methyl-9-phenylacridine iodide usage as a photocatalyst in the process of molecular hydrogen evolution in various aprotic solvents has...     

Chaos in a tethered satellite system induced by atmospheric drag and Earth’s oblateness

Nonlinear Dynamics - This paper describes the chaos behavior of an in-plane tethered satellite system induced by atmospheric drag and the Earth’s oblateness. A commonly used model, the...     

Surface Conductivity of the Ytterbium-Doped Topological Kondo-Insulator SmB6

Doklady Physics - The temperature dependence of the conductivity of the topological Kondo-insulator (TKI) Sm1 – xYbxB6 is investigated in the temperature range 2 < T < 300 K for...     

An Elementary Dipole Emitter Located Either on the Boundary of a Layered Structure or Inside It

Optics and Spectroscopy - A rigorous theory of radiation of an elementary dipole that is located either on the boundary of a plane-layered structure or inside it is considered. For a particular...     

Thin-Film Nonlinear Optical Crystals for Intracavity Electro-Optic Modulation

Optics and Spectroscopy - Methods of preparation of single-crystal 4-N,N-dimethylamino-4′-N′-methyl stilbazolium tosylate (DAST) films with a thickness of several micrometers, designed...