Structural Properties and Magnetic Ground States of 100 Binary d-Metal Oxides Studied by Hybrid Density Functional Methods.

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.

Negative thermal expansion of Cu2O studied by quasi-harmonic approximation and cubic force-constant method.

Cubic cuprous oxide, Cu2O, 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 Cu2O. 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 Cu2O are correctly reproduced up to 500 K, with a slight overall underestimation of the volume contraction.

Thermoelectric Properties of p-Type Cu2O, CuO, and NiO from Hybrid Density Functional Theory.

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.

Lithium Aryloxide Thin Films with Guest-Induced Structural Transformation by ALD/MLD.

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.

Synthesis, structure and photophysical properties of a highly luminescent terpyridine-diphenylacetylene hybrid fluorophore and its metal complexes.

A new fluorescent terpyridyl-diphenylacetylene hybrid fluorophore 4'-[4-{(4-methoxyphenyl)ethynyl}phenyl]-2,2':6',2''-terpyridine, L, was synthesized via Sonogashira cross-coupling of 4'-(4-bromophenyl)-2,2':6',2''-terpyridine and 4-ethynylanisole in the presence of Pd(PPh3)4/CuI as a catalyst. The solid state structure of L shows a trans arrangement of pyridine nitrogen atoms along the interannular bond in the terpyridine domain. Five transition metal complexes of L, {[FeL2](CF3SO3)2 (1), [ZnL2](ClO4)2 (2), [CdL2](ClO4)2 (3), [RuL2](PF6)2 (4), and PtMe3IL (5)}, have also been synthesized and characterized by spectroscopic methods and single crystal X-ray analysis. The X-ray crystal structures of complexes 1-3 show a distorted octahedral MN6 arrangement with tridentate coordination of the two terpyridine ligands, whereas in complex 5 the ligand L binds in a bidentate fashion. The ligand L displays bright blue emission in the solid state and in both non-polar and polar organic media. The fluorescence quantum yield of L is exceptionally high for a monoterpyridine ligand of its kind, which can be rationalized with density functional theory calculations. The electronic structure of L shows that the fluorescence involves intramolecular charge transfer from the diphenylacetylene moiety to the terpyridine group, and it is not affected by the usual non-radiative relaxation processes such as pyridine rotation. The Fe(II), Ru(II) and Pt(IV) complexes of L were found to be non-emissive, whereas both Zn(II) and Cd(II) complexes displayed significant green emission attributed to intra-ligand charge transfer states. These results were supported by the observed red-shift of the emission maxima of complexes 2 and 3 with increasing the solvent polarity.