Clustering and Halogen Effects Enabled Red/Near-Infrared Room Temperature Phosphorescence from Aliphatic Cyclic Imides

<a>Pure organics with room temperature phosphorescence (RTP) are urgently demanded in advanced optoelectronic and bioelectronic applications. However, currently reported phosphors are mostly aromatics and restricted to blue to orange colors. It remains an enormous challenge to achieve red and near-infrared (NIR) RTP, particularly for those from nonaromatics. Here we demonstrate a series of cyclic imides derived from succinimide, which can emit red (665, 690 nm) and even NIR (745 nm) RTP with outstanding efficiencies of up to 9.2%, despite their rather limited molecular conjugations. Such unique emission should be ascribed to the presence of the imide unit and heavy atoms, effective molecular clustering, and the electron delocalization of halogens, which not only greatly facilitate intersystem crossing, but also afford significantly extended through-space conjugation and rigidified conformations.</a> These results pave the way to the rational construction of red and NIR nonconventional luminophores through synergistic clustering and halogen effects.

Relativistic Configuration-Interaction and Perturbation Theory Calculations for Heavy Atoms

Heavy atoms present challenges to atomic theory calculations due to the large number of electrons and their complicated interactions. Conventional approaches such as calculations based on Cowan’s code are limited and require a large number of parameters for energy agreement. One promising approach is relativistic configuration-interaction and many-body perturbation theory (CI-MBPT) methods. We present CI-MBPT results for various atomic systems where this approach can lead to reasonable agreement: La I, La II, Th I, Th II, U I, Pu II. Among atomic properties, energies, g-factors, electric dipole moments, lifetimes, hyperfine structure constants, and isotopic shifts are discussed. While in La I and La II accuracy for transitions is better than that obtained with other methods, more work is needed for actinides.

Towards the automatic crystal structure solution of nucleic acids: automated model building using the new CAB program

CAB, a recently described automated model-building (AMB) program, has been modified to work effectively with nucleic acids. To this end, several new algorithms have been introduced and the libraries have been updated. To reduce the input average phase error, ligand heavy atoms are now located before starting the CAB interpretation of the electron-density maps. Furthermore, alternative approaches are used depending on whether the ligands belong to the target or to the model chain used in the molecular-replacement step. Robust criteria are then applied to decide whether the AMB model is acceptable or whether it must be modified to fit prior information on the target structure. In the latter case, the model chains are rearranged to fit prior information on the target chains. Here, the performance of the new AMB program CAB applied to various nucleic acid structures is discussed. Other well documented programs such as Nautilus, ARP/wARP and phenix.autobuild were also applied and the experimental results are described.

Engineering the sensitivity of macroscopic physical systems to variations in the fine-structure constant

Experiments aimed at searching for variations in the fine-structure constant α are based on spectroscopy of transitions in microscopic bound systems, such as atoms and ions, or resonances in optical cavities. The sensitivities of these systems to variations in α are typically on the order of unity and are fixed for a given system. For heavy atoms, highly charged ions and nuclear transitions, the sensitivity can be increased by benefiting from the relativistic effects and favorable arrangement of quantum states. This article proposes a new method for controlling the sensitivity factor of macroscopic physical systems. Specific concepts of optical cavities with tunable sensitivity to α are described. These systems show qualitatively different properties from those of previous studies of the sensitivity of macroscopic systems to variations in α, in which the sensitivity was found to be fixed and fundamentally limited to an order of unity. Although possible experimental constraints attainable with the specific optical cavity arrangements proposed in this article do not yet exceed the present best constraints on α variations, this work paves the way for developing new approaches to searching for variations in the fundamental constants of physics.

LANTHANIDE COMPLEXES WITH REGIOISOMERS OF CHLORO-SUBSTITUTED TETRAPHENYLPORPHYRIN

Several isomeric complexes of Yb (III) and Lu(III) with H2tpp and its tetrachloro-substituted derivatives were synthesized. Symmetrical ortho-, meta- and para-positioning of four heavy atoms allows to study their effect on emission features of complexes. Obtained results show the rise of 4f-luminescence effectiveness in the row ortho-meta-para isomers.

Optimizing reaction coordinate by flux maximization in the transition path ensemble

Transition path ensemble is a collection of reactive trajectories, all of which largely keep going forward along the transition channel from the reactant state to the product one, and is believed to possess the information necessary for the identification of reaction coordinate. Previously, the full coordinates (both position and momentum) of the snapshots in the transition path ensemble were utilized to obtain the reaction coordinate (J. Chem. Phys. 2016, 144, 114103; J. Chem. Phys. 2018, 148, 084105). Here, with the conformational (or position) coordinates alone, it is demonstrated that the reaction coordinate can be optimized by maximizing the flux of a given coordinate in the transition path ensemble. In the application to alanine dipeptide in vacuum, dihderal angles ϕ and θ were identified to be the two best reaction coordinates, which was consistent with the results in existing studies. A linear combination of these two coordinates gave a better reaction coordinate, which is highly correlated with committor. Most importantly, the method obtained a linear combination of pairwise distances between heavy atoms, which was highly correlated with committor as well. The standard deviation of committor at the transition region defined by the optimized reaction coordinate is as small as 0.08. In addition, the effects of practical factors, such as the choice of transition path sub-ensembles and saving interval between frames in transition paths, on reaction coordinate optimization were also considered.

Determining the ratio of the number of recoil electrons to the number of photoelectrons using a new method

The problem in question is relevant due to discrepancy between the results of theoretical and known experimental studies of various interactions of ionizing emission photons with substances, in particular, photo effect and Compton scattering of these photons. The study aimed at carrying out specific measurements using a new method of simultaneously determining the ratio of the number of recoil electrons to the number of photoelectrons. Analysis of the results showed that there are significant discrepancies between theoretical calculations and experimental data. New values of simultaneously measured ratios of cross-sections for heavy atoms using a method invented by the author, and old measurements of these ratios for light atoms usingWilson cloud chamber, when compared with theoretical calculations, show that a significant (by one order and more) one-direction discrepancy is seen for X-ray and gamma emissions over a range of energies in question.It is shown that these discrepancies might be attributed to the fact that an atomic electron is in a free state for a while. Compton scattering occurs with a free electron; photo effect involves only bound electrons. Therefore, Compton scattering cross section is proportional to a period of time, during which electron was in a free state, whereas photo effect cross section is proportional to a time period, during which electron was in a bound state. The article materials might be helpful to perform both fundamental, and applied studies on interaction of light quanta with substance including modelling the phenomena under examination.

Design and realization of topological Dirac fermions on a triangular lattice

Large-gap quantum spin Hall insulators are promising materials for room-temperature applications based on Dirac fermions. Key to engineer the topologically non-trivial band ordering and sizable band gaps is strong spin-orbit interaction. Following Kane and Mele’s original suggestion, one approach is to synthesize monolayers of heavy atoms with honeycomb coordination accommodated on templates with hexagonal symmetry. Yet, in the majority of cases, this recipe leads to triangular lattices, typically hosting metals or trivial insulators. Here, we conceive and realize “indenene”, a triangular monolayer of indium on SiC exhibiting non-trivial valley physics driven by local spin-orbit coupling, which prevails over inversion-symmetry breaking terms. By means of tunneling microscopy of the 2D bulk we identify the quantum spin Hall phase of this triangular lattice and unveil how a hidden honeycomb connectivity emerges from interference patterns in Bloch px ± ipy-derived wave functions.