Dejan Zagorac

Sterically Active Electron Pairs in Lead Sulfide? An Investigation of the Electronic and Vibrational Properties of PbS in the Transition Region Between the Rock Salt and the α‐GeTe‐Type Modifications

Recently, we have investigated the energy landscape of PbS for many different pressures on the ab initio level by using Hartree-Fock and density functional theory to globally search for possible thermodynamically stable and metastable structures. The perhaps most fascinating observation was that besides the experimentally known modification exhibiting the rock salt structure a second minimum exists close-by on the landscape showing the low-temperature α-GeTe-type structure. In the present study, we investigate the possible reasons for the existence of this metastable modification; in particular we address the question, whether the α-GeTe-type modification might be stabilized (and conversely the rock salt modification destabilized) by steric effects of the non-bonding electron pair.

Theoretical investigations of novel zinc oxide polytypes and in-depth study of their electronic properties

Zinc oxide is one of the most investigated compounds in materials science, both experimentally and theoretically, while in nature it appears only rarely, as the mineral zincite. Yet there are still many open questions: Is it still possible to observe or synthesize new modifications of zinc oxide? And can we improve the properties of a material that has already been investigated in thousands of studies? What is the connection between zincite, zinc sulfide and zinc oxide, and can we finally explain the controversial mineral matraite? In short, Yes: the answer to these questions is polytypism. We identify a multitude of possible stable polytypes for zinc oxide, and we show that by varying the stacking order, we can fine-tune the electronic properties such as the direct primary and secondary band gaps in zinc oxide without adding dopant atoms.

Prediction of possible CaMnO3 modifications using an ab initio minimization data-mining approach

We have performed a crystal structure prediction study of CaMnO3 focusing on structures generated by octahedral tilting according to group-subgroup relations from the ideal perovskite type (Pm\overline 3 m), which is the aristotype of the experimentally known CaMnO3 compound in the Pnma space group. Furthermore, additional structure candidates have been obtained using data mining. For each of the structure candidates, a local optimization on the ab initio level using density-functional theory (LDA, hybrid B3LYP) and the Hartree--Fock (HF) method was performed, and we find that several of the modifications may be experimentally accessible. In the high-pressure regime, we identify a post-perovskite phase in the CaIrO3 type, not previously observed in CaMnO3. Similarly, calculations at effective negative pressure predict a phase transition from the orthorhombic perovskite to an ilmenite-type (FeTiO3) modification of CaMnO3.

Barium Sulfide under Pressure: Discovery of Metastable Polymorphs and Investigation of Electronic Properties on ab Initio Level

Barium sulfide (BaS) is an important precursor to other barium compounds with applications from ceramics and flame retardants to luminous paints and additives, and recent research shows potential technological applications in electrical and optical devices. Under normal conditions, BaS crystallizes in the NaCl type of structure, and with the increase in pressure BaS undergoes a structural phase transition to a CsCl type modification. This study presents modeling of barium sulfide under pressure with special focus on structural aspects and electronic properties. We predict metastable BaS polymorphs which have not yet been observed in the experiment or in previous calculations, and we investigated their vibrational and thermodynamical properties. Furthermore, we investigate the electronic properties of experimentally known structures as well as novel predicted modifications of BaS on ab initio level using Hartree-Fock, GGA-PBE, and the hybrid B3LYP functional. In this way, we address new possibilities of synthesizing BaS and possible band gap tuning which can have great applications in optoelectrical technologies.

Structural study of nanosized yttrium-doped CaMnO3 perovskites

Nanostructured compounds with general formula Ca1–xYxMnO3 (0 ≤ x ≤ 1) were synthesized by modified glycine nitrate procedure. In the next step, we have investigated crystal structure and microstructure of the synthesized samples using X-ray methods and Rietveld analysis. Focus of this research was the structural stability of the yttrium-doped CaMnO3 perovskite phases, which crystallize in orthorhombic space group Pnma. We observed that the unit cell volumes of the investigated compounds increase proportionally with yttrium amount. Furthermore, we investigated the influence of yttrium amount on Mn–O bond angles and distances, tilting of MnO6 octahedra and deformation due to the presence of Jahn–Teller distortion around Mn3+ cation. In order to estimate effective coordination of A and B sites, bond valence calculations (BVC) were performed for A and B site cations. Finally, the photoelectron spectroscopy (XPS) method was applied in order to follow yttrium concentration in the perovskite phases.