Recent insights for achieving mixed halide perovskites without halide segregation

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Intra‐ and Intermolecular Dispersion Interactions in [n]Cycloparaphenylenes: Do They Influence Their Structural and Electronic Properties?

Cycloparaphenylenes (CPPs) are nanosized structures with unique isolated and bulk properties, and are synthetic targets for the template‐driven bottom‐up synthesis of carbon nanotubes. Thus, a systematic understanding of the supramolecular order at the nanoscale is of utmost relevance for molecular engineering. In this study, it is found that intramolecular noncovalent (dispersion) interactions must be taken into account for obtaining accurate estimates of the structural and optoelectronic properties of [n]CPP compounds, and their influence as the number of repeat units increases from n=4 to n=12 is also analyzed, both in the gas phase and in solution. The supramolecular self‐assembly, for which both intra‐ and intermolecular noncovalent interactions are relevant, of [6]CPP is also investigated by calculating the binding energies of dimers taken along several crystal directions. These are also used to estimate the cohesive energy of the crystal, which is compared to the value obtained by means of dispersion‐corrected DFT calculations using periodic boundary conditions. The reasonable agreement between both computational strategies points towards a first estimate of the [6]CPP cohesive energy of around 50 kcal mol^?1.     

Finite Element Modeling of Liquid Deuterium Flow and Heat Transfer in a Cold-neutron Source

A finite element simulation of flow and heat transfer in the moderator cell of a cold-neutron source (CNS), in which liquid deuterium subject to internal heat generation is flowing, is reported. The numerical scheme consists of a stabilized equal-order method. A time-accurate approach is adopted to resolve the large-scale eddies of the flow, with a Smagorinsky's model for the subgrid-scale effects. The thermal coupling follows a staggered strategy, with SUPG-type upwinding. A specific wall-law is developed that accounts for the correct partition of the heat deposited at the wall by radiation between the liquid deuterium and the helium gas flowing at the outer side of the wall. The average flow and thermal structure are presented. The turbulent fluctuations are both illustrated in physical space and decomposed into spectral components. The wavenumber spectrum suggests that adequate resolution of the large-scale eddies has been attained with just 200,000 nodes, while a DNS analysis would have required at least 1010 nodes. Usefulness of the approach in the design process of the CNS is highlighted.     

Influence of Majorana Bound States in Quantum Rings

A quantum ring coupled to a 1D topological superconductor hosting Majorana bound states (MBSs) is investigated. The MBSs effects over the spectrum and persistent current along the quantum ring are studied. The spectra of the system are obtained by an exact numerical diagonalization of the Bogoliubov-de Gennes Hamiltonian in the Majorana representation. In addition, Green's function formalism is implemented for analytical calculations and obtained a switching condition in the MBSs fermionic parity. Three different patterns that could be obtained for the spatial separation of the MBSs, named: bowtie, diamond, and asymmetric, are reported here, which are present only in odd parity in the quantum ring, while only a single pattern (bowtie) is obtained for even parity. Those patterns are subject strictly to the switching condition for the MBSs. Besides, quantum ring with the presence of a Majorana zero mode presents gapped/gapless spectra in odd/even parity showing in the even case a subtle signature in the persistent current.     

Computational NMR coupling constants: Shifting and scaling factors for evaluating 1JCH

Optimized shifting and/or scaling factors for calculating one‐bond carbon–hydrogen spin–spin coupling constants have been determined for 35 combinations of representative functionals (PBE, B3LYP, B3P86, B97‐2 and M06‐L) and basis sets (TZVP, HIII‐su3, EPR‐III, aug‐cc‐pVTZ‐J, ccJ‐pVDZ, ccJ‐pVTZ, ccJ‐pVQZ, pcJ‐2 and pcJ‐3) using 68 organic molecular systems with 88 ¹J_CH couplings including different types of hybridized carbon atoms. Density functional theory assessment for the determination of ¹J_CH coupling constants is examined, comparing the computed and experimental values. The use of shifting constants for obtaining the calculated coupling improves substantially the results, and most models become qualitatively similar. Thus, for the whole set of couplings and for all approaches excluding those using the M06 functional, the root‐mean‐square deviations lie between 4.7 and 16.4 Hz and are reduced to 4–6.5 Hz when shifting constants are considered. Alternatively, when a specific rovibrational contribution of 5 Hz is subtracted from the experimental values, good results are obtained with PBE, B3P86 and B97‐2 functionals in combination with HIII‐su3, aug‐cc‐pVTZ‐J and pcJ‐2 basis sets. Copyright © 2013 John Wiley & Sons, Ltd.     

Novel coordination compounds of quinic acid. X-ray diffraction study of copper(II) complexes where the metal ion was a chiral centre

Summary The synthesis and characterization of the following coordination compounds derived from quinic acid (quin) (1): [Cu(quin)Cl(H₂O)]_n·(H₂O)_n(2); [Ni(quin)Cl(H₂O)]_n·(2H₂O) n (3); [Co(quin) Cl(H₂O)]_n·(2H₂O)_n(4); [Cu(quin) (NO₃)(H₂O)]_n·(2H₂O)_n(5); [Cu(quin)(AcO)(H₂O)]_n· (2H₂O)_n(6); [Cu(quin)H₂O]₂·2H₂O(7); [Co(quin)₂]_n (8); [Zn(quin)₂](9); [Cd(quin)₂](10) and [Hg(quin)₂]· 4H₂O (11) is presented. All of the compounds were characterized by i.r. and u.v. spectroscopy; in addition, (9) and (10) were analysed by n.m.r., and (2), (5) and (7) by X-ray crystallography. Due to the polyfunctionality of quinic acid diverse structures were obtained: (2) –(6) and (8) were polymeric, (7) was dimeric and (9) –(11) were spiranic. In compound (2) the Cu had a distorted octahedral structure; it was a chiral centre with six different substituents and an optically active ligand. Only one stereoisomer (OC-6-25-A) of the 30 possible was observed in the crystal. Compound (5) was also polymeric, the hexacoordinated Cu atom was a chiral centre (OC-6-53C) and only one stereoisomer was observed. It was bonded to three quinic acid ligands in three different coordination modes and each quinic acid was in turn bonded to three different Cu atoms. Each chain was linked to another two chains giving a net structure. Compound (7) was a dimer with two square pyramidal Cu atoms. Two apical water molecules were found in acis arrangement. Each quinic acid ligand was bonded to two Cu atoms which were linked by two oxygen bridges and each Cu atom was bonded to two quinic acid moieties.     

Interactions of metal‐encapsulated fullerenes with solvents

The present investigation reports on the interaction of M@C₆₀(M = Be, Mg, Ca) with solvents (H₂O, CH₃OH, HF, NH₃) using Density Functional Theory calculations. Our computations reveal that the interaction of the fullerene species increases when endohedral metal atoms are inserted into its cavity. The most profound interaction of the fullerene systems is with water and hydrogen fluoride. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

Focused ion beam preparation of atom probe specimens containing a single crystallographically well-defined grain boundary

Needle-shaped atom probe specimens containing a single grain boundary were produced using the focused ion beam (FIB) of a two-beam FIB/SEM (scanning electron microscope) system. The presented specimen preparation approach allows the unprecedented study of a grain boundary which is well characterised in its crystallographic orientation by means of the field ion microscope (FIM) and the tomographic atom probe (TAP). The analysis of such specimens allows in particular the determination of solute excess atoms at this specific grain boundary and hence the investigation of the segregation behaviour. The crucial preparation steps are discussed in detail in the present study for the Sigma 19 a {331} 110 grain boundary of a 40 at.ppm-Bi doped Cu bi-crystal. Transmission electron microscope (TEM) images and TAP analyses of the atom probe tips demonstrate unambiguously the presence of the selectively prepared grain boundary in the apex region of some of the specimens.     

Entropy generation in cosmological particle creation

A very simplified model of the Universe is considered in order to propose an alternative approach to the irreversible evolution of the Universe at very early times. The entropy generation at the quantum stage can be thought of as a consequence of an instability of the system. Then particle creation arises from this instability.