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Bright luminescence of Eu(ii) doped into the cubic perovskites KMgH3 and mixed crystal compounds LiBaxSr1−xH3 was observed and assigned to the 4f65d–4f7 emission of Eu2+. KMgH3:Eu2+ shows an extremely bright yellow emission, whereas the wavelength of the emission maximum in LiBaxSr1−xH3:Eu2+ depends on the value of x and ranges from yellow to green. Furthermore, an extremely wide red shift in the emission energy is observed for the orthorhombically distorted perovskite NaMgH3:Eu2+. Additionally, we review the crystal structure of KMgH3 using density functional calculations. [ABSTRACT FROM AUTHOR]

In this paper we develop the shape effect, which is relevant for crystalline materials whose size is larger than that of the thermodynamic limit. According to this effect the electronic properties of one surface of a crystal depend upon all of its surfaces, i.e. on the overall shape. At first, qualitative mathematical arguments are presented for the existence of this effect based on the conditions for the stability of polar surfaces. Our treatment explains why such surfaces are observed even though earlier theory indicated that they should not exist. Then, models are developed from which it is found computationally that changing the shape of a polar crystal can substantially alter the magnitude of its surface charges. Apart from surface charges, it follows that the crystal shape will also significantly affect bulk properties, most notably polarization and piezoelectric responses. Additional model calculations show a strong shape effect on the activation energy for heterogeneous catalysis primarily through local surface charges rather than a non-local/long range electrostatic potential.

Stimulated by the early theoretical prediction of B 80 fullerene and the experimental finding of the B 40 cage, the structures of medium-sized boron clusters have attracted intensive research interest during the last decade, but a complete picture of their size-dependent structural evolution remains a puzzle. Using a genetic algorithm combined with density-functional theory calculations, we have performed a systematic global search for the low-lying structures of neutral B n clusters with n = 31-50. Diverse structural patterns, including tubular, quasi-planar, cage, core-shell, and bilayer, are demonstrated for the ground-state B n clusters; for certain cluster sizes, unprecedented geometries are predicted for the first time. Their stabilities at finite temperatures are evaluated, and the competition mechanism between various patterns is elucidated. Chemical bonding analysis reveals that the availability of localized σ bonds and delocalized π bonds in the B n clusters play a key role in their structural stability. Our results provide important insights into the bonding pattern and growth behavior of medium-sized boron clusters, which lay the foundation for experimental design and synthesis of boron nanostructures.

The C-H functionalization is very important for the synthesis of pharmaceuticals and complex natural products. Rhodium carbenoids, obtained when a dirhodium(ii) catalyst containing a crown formed by chiral ligands reacts with diazo compounds with both an electron donating group and an electron withdrawing group, play an important part in controlling site- and enantio-selectivity for functionalization of non-activated C-H bonds. It has earlier been demonstrated that the tertiary C-H bond is more favored to be functionalized inside the crown of the dirhodium catalyst with S-configuration ligands compared with the secondary and primary C-H bonds although the latter possess weaker steric effects. We argue that the higher site- and enantio-selectivity for some types of C-H bond functionalization can be related to intermolecular hydrogen bonding, steric hindrance, and weak interactions when the dirhodium catalyst is interacting with the chiral ligands.

A systematic investigation is performed on the electronic transport properties of armchair-graphene nanoribbon (AGNR) heterojunctions using spin-polarized density functional theory calculations in combination with the non-equilibrium Green's function formalism. 9-AGNR and 5-AGNR structures are used to form a single-well configuration by sandwiching a 5-AGNR between two 9-AGNRs. At the same time, these 9-AGNRs are matched at the left and right to electrodes, 9 and 5 being the number of carbon dimers as width. This heterojunction mimics an electronic device with two potential barriers (9-AGNR) and one quantum well (5-AGNR) where quasi-bound states are confined. First, we study the ground state properties, and then we calculate the electron transport properties of this device as a function of the well width. We show the presence of electronic tunnelling resonances between the barriers by delocalized electron density inside the well's structure. This is corroborated by transmission curves, localized densities of states (LDOS), current-vs.-bias voltage results, and the trend of the resonances as a function of the well width. This work shows that carbon AGNRs may be used as resonant-tunnelling devices for applications in nanoelectronics.

Dye-sensitized solar cells (DSSCs) have attracted much interest during the past few decades. However, it is still a tremendous challenge to identify organic molecules that give an optimal power conversion efficiency (PCE). Here, we apply our recently developed, inverse-design method for this issue with the special aim of identifying porphyrins with promisingly high PCE. It turns out that the calculations lead to the prediction of 15 new molecules with optimal performances and for which none so far has been studied. These porphyrin derivatives will in the near future be synthesized and subsequently tested experimentally. Our inverse-design approach, PooMa, is based on the strategy of providing suggestions for molecular systems with optimal properties. PooMa has been developed as a tool that requires minimal resources and, therefore, builds on various approximate methods. It uses genetic algorithm to screen thousands (or often more) of molecules. For each molecule, the density-functional tight-binding (DFTB) method is used for calculating the electronic properties. In the present work, five different electronic properties are determined, all of which are related to optical performance. Subsequently, a quantitative structure-property relationship (QSPR) model is constructed that can predict the PCE through those five electronic properties. Finally, we benchmark our results through more accurate DFT calculations that give further information on the predicted optimal molecules.

The canonical thermodynamics of clusters is determined quantum mechanically in the general case of multiple minima of the potential energy surface (PES) using the superposition approximation. As an illustration of the consequences of our approach, we study in detail the thermodynamic properties of CuN clusters with N from 2 to 150 as a function of cluster size, temperature, and number of isomers. Thereby, for instance, solid-solid transition temperatures for several cluster sizes are determined. We show that the cluster vibrations have a strong impact on the stability of the clusters and that this can be observed not only at medium and high temperatures but also at low temperatures and even at T = 0 K. Thus, including zero-point corrections can change the relative energetic ordering of different isomers. This isomeric effect results in an oscillatory dependence of the heat capacity on cluster size at moderate and high temperatures. Moreover, for the identification of magic clusters at non-vanishing temperature, the Helmholtz free energy is analyzed as a function of cluster size and temperature within a one-, two-, and three-minima model of the PES. Thereby, we demonstrate that the concept of magic clusters is strongly temperature dependent so that in several cases clusters change from being magic or non-magic at T = 0 K to be the opposite at non-vanishing temperature. We emphasize that all these effects are not specific for copper clusters alone but can also be observed in other metal or semiconductor nanoclusters.

The vibrational spectrum ω i of a re-optimized neutral gold cluster Au 58 has been calculated using a numerical finite-difference approach and the density-functional tight-binding (DFTB) method. We have exactly predicted the vibrational frequency ranging from 3.88 through to 304.49 cm -1 which depends on the size and the arrangement of the atoms in the nanoparticle morphology of the cluster at Δ E = 0. Our investigation has revealed that the vibrational spectrum is strongly influenced by size and structure. It is well known that gold atomic clusters can have planar or hollow cage-like structures due to their relativistic effect. However, in our study, by first principles calculations on a Au 58 cluster we have proposed that gold clusters of medium size can form a shell-like structure (skeleton/helmet), this is demonstrated by the remarkable robustness of a double shell structure with a hollow inner shell of about ten atoms. Finally, the structure symmetry ( C 1 ) is confirmed through the cluster size, vibrational spectroscopy, and by studying the effect of temperature on a neutral gold cluster for the first time., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The contribution of surface units to bulk properties are often neglected in theoretical and computational studies of crystalline systems. We demonstrate that this assumption has to be made with caution in the case of (electric field) polarization. As a generalization of an earlier work on quasi-one-dimensional systems [Springborg, et al., Phys. Rev. B: Condens. Matter Mater. Phys., 2010, 82, 165442], it is shown that the polarization for 2D and 3D systems contains a surface contribution that can, in principle, take any value (within physical limits) and has consequences for converse piezoelectric responses. Subsequently, we determine the surface effects quantitatively for a group of ferroelectric perovskite structures. Our results indicate that such contributions can be substantial.

Using two different approaches, the structures of Cd n clusters are optimized. At first, parameterized density-functional calculations using the DFTB method in combination with evolutionary algorithms provide one set of candidate structures. Second, earlier proposed structures based on the Gupta potential provide a second set. Subsequently, all structures of each set are re-optimized using parameter-free density-functional calculations. It turned out that those based on the DFTB calculations in almost all cases were those of the lowest total energy. By analysing the structural properties as a function of cluster size information on growth patterns can be extracted. Thereby, the results show a certain preference that the atoms of the inner parts have surroundings as found in bulk hcp Cd. Furthermore, for larger size ranges, we could identify a specific growth pattern, implying that most of these clusters cannot be classified as being disordered. The results show also that the 4d electrons have only a weak influence on the properties of the clusters that, however, is so strong that a jellium-like model occasionally becomes inaccurate in describing the properties. In particular, the question at which size the clusters can be considered to be metallic becomes non-trivial to answer. Further arguments based on a comparison of the HOMO-LUMO gaps with the Kubo gap, however, suggested the non-metallic properties in the studied size range.

A crystalline material formed by parallel chains of silver atoms inside one-dimensional tunnels of hollandite manganese dioxide, Ag-αMnO2, is investigated through first-principles total energy calculations. Two different magnetic phases have been identified; one structure containing linear Ag chains with an antiferromagnetic ordering in the direction perpendicular to the MnO2 tunnels for T = 0 K (I4/m) and another configuration with zigzag Ag chains in a non-magnetic regime for higher temperatures (P21/c). According to phonon dispersions, both structures are stable. On the other hand, the structure with linear Ag chains in the non-magnetic state is unstable. A critical temperature of Tc≃ 125 K for the magnetostructural phase transition between the two stable structures I4/m and P21/c is predicted.

We report a straightforward synthesis of 8-ethynyl-BODIPY derivatives and their potential as fluorescent labeling compounds using an alkyne-azide click chemistry approach. The ethynyl substituted BODIPY dyes at the meso-position were reacted under Cu(+) catalysis and mild physiological conditions in organic and biological model systems using benzyl azide and a Barstar protein which was selectively modified by a single amino acid substituted methionine at the N-terminus (Met1) → azidohomoalanine (Aha). Conjugation with the protein and the model azide was indicated by a significant blue shift upon formation of the triazole moiety system, which allowed easy distinction between free and coupled dyes. This blue shift was rationalized by the perpendicular orientation of the triazole relative to the chromophore using time dependent density functional theory (TDDFT) calculations. A full spectroscopic and thermodynamic characterization of the protein revealed that a fluorophore was incorporated without the cross influence of protein stability and functional integrity. Furthermore, model reactions of 8-ethynyl-BODIPY derivatives with benzyl azide under copper-free conditions indicate second order kinetics with high rate constants comparable with those found for the strain-promoted azide-alkyne cycloaddition (SPAAC). In this way, we establish a unique and highly efficient method to introduce alkyne-BODIPY into a protein scaffold potentially useful for diverse applications in areas ranging from fundamental protein dynamics studies to biotechnology or cell biology.

Using a parameter-free, density-functional method that has been developed explicitly for the theoretical treatment of infinite, periodic, isolated, helical polymers we study various polymers related to polythiophene. In particular we discuss how the electronic properties of polythiophene are changed when replacing some of the H atoms by CH3 group, by incorporating vinylene bridges into the backbone, or when replacing some or all the CH units of the backbone by N atoms. We observe the weakest effects for the methyl-substitution and the strongest for the N-incorporation. The latter leads to an overall downward shift of all bands, but in contrast to the case for polyacetylene, the unrelaxed compound with N atoms does not have N lone-pair orbitals as the highest occupied ones. Instead these occur at somewhat deeper energies. When comparing the aromatic and quinoid forms we found for the pure compound as well as for the methyl-containing one that the gap closes when passing from the one to the other form which was not found for any of the other materials of the present study. Moreover, the energy of the HOMO was found to depend stronger on the bond-length alternation than the energy of the LUMO, ultimately giving that polarons will induce two asymmetrically placed gap states with the energetically lower one appearing deeper in the gap than the other one.