The lattice thermal conductivity of Cu 2 O was studied using ab initio density functional methods. The performance of generalized gradient approximation (GGA), GGA-PBE, and PBE0 exchange-correlation functionals was compared for various electronic and phonon-related properties. The 3d transition metal oxides such as Cu 2 O are known to be a challenging case for pure GGA functionals, and in comparison to the GGA-PBE the PBE0 hybrid functional clearly improves the description of both electronic and phonon-related properties. The most striking difference is found in the lattice thermal conductivity, where the GGA underestimates it as much as 40% in comparison to experiments, while the difference between the experiment and the PBE0 hybrid functional is only a few percent.

A new fluorescent terpyridyl-diphenylacetylene hybrid chromophore is reported. The fluorophore displays bright blue emission with an exceptionally high quantum yield.

Crystalline Li–organic thin films are grown with the atomic/molecular layer deposition (ALD/MLD) technique from lithium hexamethyldisilazide and hydroquinone. The as‐deposited films are found to undergo a reversible structural transformation upon exposure to ambient humid air. According to density functional theory calculations, the guest‐induced transformation may be related to an unsaturated Li site in the crystal structure.

The electronic transport coefficients of three Earth-abundant metal oxides Cu2O, CuO, and NiO were investigated using hybrid density functional theory (DFT). Hybrid DFT methods combined with local Gaussian-type basis sets enabled band structure studies on both non-magnetic and magnetic p-type metal oxides without empirical corrections. The CRYSTAL code was used for obtaining the wavefunction, and the transport properties were calculated with two different methodologies to benchmark their accuracy: a numerical approach as implemented in the BoltzTraP code and an analytical approach recently implemented in CRYSTAL17. Both computational methods produce identical results in good agreement with experimental measurements of the Seebeck coefficient. The predicted electrical conductivities are overestimated, owing likely to the used approximation of a constant electronic relaxation time in the calculations, as explicit electron scattering is neglected and relaxation time is considered only as a free parameter. The obtained results enable us to critically review and complement the available theoretical and experimental literature on the studied p-type thermoelectric metal oxide materials.

d-metal oxides play a crucial role in numerous technological applications and show a great variety of magnetic properties. We have systematically investigated the structural properties, magnetic ground states, and fundamental electronic properties of 100 binary d-metal oxides using hybrid density functional methods and localized basis sets composed of Gaussian-type functions. The calculated properties are compared with experimental information in all cases where experimental data are available. The used PBE0 hybrid density functional method describes the structural properties of the studied d-metal oxides well, except in the case of molecular oxides with weak intermolecular forces between the molecular units. Empirical D3 dispersion correction does not improve the structural description of the molecular oxides. We provide a database of optimized geometries and magnetic ground states to facilitate future studies on the more complex properties of the binary d-metal oxides.

Cubic cuprous oxide, Cu 2 O, is characterized by a peculiar structural response to temperature: it shows a relatively large negative thermal expansion below 250 K, then followed by a positive thermal expansion at higher temperatures. The two branches of its thermal expansion (negative and positive) are almost perfectly symmetric at low temperatures, with the minimum of its lattice parameter at about 250 K and with the lattice parameter at 500 K almost coinciding with that at 0 K. We perform lattice-dynamical quantum-mechanical calculations to investigate the thermal expansion of Cu 2 O. Phonon mode-specific Grüneisen parameters are computed, which allows us to identify different spectral regions of atomic vibrations responsible for the two distinct regimes of thermal expansion. Two different computational approaches are explored, their results compared, and their numerical aspects critically assessed: a well-established method based on the quasiharmonic approximation, where harmonic frequencies are computed at different lattice volumes, and an alternative approach, where quadratic and cubic interatomic force-constants are computed at a single volume. The latter scheme has only recently become computationally feasible in the context of lattice thermal conductivity simulations. When proper numerical parameters are used (phonon sampling, tolerances, etc.), the two approaches are here shown to provide a very consistent description, yet at a rather different computational cost. All of the experimentally observed features of the complex thermal expansion of Cu 2 O are correctly reproduced up to 500 K, with a slight overall underestimation of the volume contraction.

The significant similarity between MF 3 , MF 4 -, and M 2 F 7 -(M = Au, Br) is studied using quantum chemical methods. It is expected that compounds containing Au 3 F 10 anions are likely to be stable. A theoretical background for the ongoing attempts of their synthesis is provided by calculations on the stabilities and molecular struc-

The reactions of heavier group 14 element alkyne analogues (EAr iPr4 )2 (E = Ge, Sn; Ar iPr4 = C6H3-2,6-(C6H3-2,6-i Pr2)2) with the group 6 transition metal carbonyls M(CO)6 (M = Cr, Mo, W)under UV irradiation resulted in the cleavage of the E-E bond and the formation of complexes {Ar iPr4 EM(CO)4}2 (1-6) that were characterized by single crystal X-ray diffraction as well as by IR and multinuclear NMR spectroscopies. Single crystal X-ray structural analyses of 1-6 showed that the complexes have a nearly planar rhomboid M2E2 core with three-coordinate group 14 atoms. The coordination geometry at the group 6 metals is distorted octahedral formed by four carbonyl groups as well as two bridging EAr iPr4 units. IR spectroscopic data suggest that the EAr iPr4 units are not very efficient -acceptors, but the investigation of E-M metal-metal interactions in 1-6 with computational methods revealed the importance of both σ-and -type contributions to bonding. The mechanism for the insertion of transition metal carbonyls into E-E bonds in (EAr iPr4 )2 was also probed computationally.2