Quantum Mechanical/Molecular Mechanical (QM/MM) Approaches

Computational modeling techniques are now standard tools in solid‐state science. They are used routinely to model and predict structures, to investigate defect, transport, and spectroscopic properties of solids, to simulate sorption and diffusion, to develop models for nucleation and growth of solids, and increasingly to model and predict reaction mechanisms. They are applied to bulk solids, surfaces, and nanostructures, and successful applications are reported for all major classes of solid: metals, semiconductors, inorganic and ceramic materials, and molecular crystals. Modeling methods are now indeed tools that are used to guide, interpret, and predict experiment

Deep vs shallow nature of oxygen vacancies and consequent n -type carrier concentrations in transparent conducting oxides

The source of n -type conductivity in undoped transparent conducting oxides has been a topic of debate for several decades. The point defect of most interest in this respect is the oxygen vacancy, but there are many conflicting reports on the shallow versus deep nature of its related electronic states. Here, using a hybrid quantum mechanical/molecular mechanical embedded cluster approach, we have computed formation and ionization energies of oxygen vacancies in three representative transparent conducting oxides: In 2 O 3 , SnO 2 , and ZnO. We find that, in all three systems, oxygen vacancies form well-localized, compact donors. We demonstrate, however, that such compactness does not preclude the possibility of these states being shallow in nature, by considering the energetic balance between the vacancy binding electrons that are in localized orbitals or in effective-mass-like diffuse orbitals. Our results show that, thermodynamically, oxygen vacancies in bulk In 2 O 3 introduce states above the conduction band minimum that contribute significantly to the observed conductivity properties of undoped samples. For ZnO and SnO 2 , the states are deep, and our calculated ionization energies agree well with thermochemical and optical experiments. Our computed equilibrium defect and carrier concentrations, however, demonstrate that these deep states may nevertheless lead to significant intrinsic n -type conductivity under reducing conditions at elevated temperatures. Our study indicates the importance of oxygen vacancies in relation to intrinsic carrier concentrations not only in In 2 O 3 , but also in SnO 2 and ZnO

Heterostructures of GaN with SiC and ZnO enhance carrier stability and separation in framework semiconductors

A computational approach, using the density functional theory, is employed to describe the enhanced electron‐hole stability and separation in a novel class of semiconducting composite materials, with the so‐called double bubble structural motif, which can be used for photocatalytic applications. We examine the double bubble containing SiC mixed with either GaN or ZnO, as well as related motifs that prove to have low formation energies. We find that a 24‐atom SiC sodalite cage inside a 96‐atom ZnO cage possesses electronic properties that make this material suitable for solar radiation absorption applications. Surprisingly stable, the inverse structure, with ZnO inside SiC, was found to show a large deformation of the double bubble and a strong localisation of the photo‐excited electron charge carriers, with the lowest band gap of ca. 2.15 eV of the composite materials considered. The nanoporous nature of these materials could indicate their suitability for thermoelectric applications. "This is the peer reviewed version of the following article: Heterostructures of GaN with SiC and ZnO enhance carrier stability and separation in framework semiconductors, which has been published in final form at https://doi.org/10.1002/pssa.201600440. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.

Thermodynamically accessible titanium clusters Ti_N, N = 2–32

We have performed a genetic algorithm search on the tight-binding interatomic potential energy surface (PES) for small TiN (N = 2–32) clusters. The low energy candidate clusters were further refined using density functional theory (DFT) calculations with the PBEsol exchange–correlation functional and evaluated with the PBEsol0 hybrid functional. The resulting clusters were analysed in terms of their structural features, growth mechanism and surface area. The results suggest a growth mechanism that is based on forming coordination centres by interpenetrating icosahedra, icositetrahedra and Frank–Kasper polyhedra. We identify centres of coordination, which act as centres of bulk nucleation in medium sized clusters and determine the morphological features of the cluster

Deep vs shallow nature of oxygen vacancies and consequent n-type carrier concentrations in transparent conducting oxides

The source of n-type conductivity in undoped transparent conducting oxides has been a topic of debate for several decades. The point defect of most interest in this respect is the oxygen vacancy, but there are many conflicting reports on the shallow versus deep nature of its related electronic states. Here, using a hybrid quantum mechanical/molecular mechanical embedded cluster approach, we have computed formation and ionization energies of oxygen vacancies in three representative transparent conducting oxides: In2O3,SnO2, and ZnO. We find that, in all three systems, oxygen vacancies form well-localized, compact donors. We demonstrate, however, that such compactness does not preclude the possibility of these states being shallow in nature, by considering the energetic balance between the vacancy binding electrons that are in localized orbitals or in effective-mass-like diffuse orbitals. Our results show that, thermodynamically, oxygen vacancies in bulk In2O3 introduce states above the conduction band minimum that contribute significantly to the observed conductivity properties of undoped samples. For ZnO and SnO2, the states are deep, and our calculated ionization energies agree well with thermochemical and optical experiments. Our computed equilibrium defect and carrier concentrations, however, demonstrate that these deep states may nevertheless lead to significant intrinsic n-type conductivity under reducing conditions at elevated temperatures. Our study indicates the importance of oxygen vacancies in relation to intrinsic carrier concentrations not only in In2O3, but also in SnO2 and ZnO

Does a ‘turbophoretic’ effect account for layer concentrations of insects migrating in the stable night-time atmosphere?

Large migrating insects, such as noctuid moths and acridoid grasshoppers, flying within the stable nocturnal boundary layer commonly become concentrated into horizontal layers. These layers frequently occur near the top of the surface temperature inversion where warm fast-moving airflows provide good conditions for downwind migration. On some occasions, a layer may coincide with a higher altitude temperature maximum such as a subsidence inversion, while on others, it may seem unrelated to any obvious feature in the vertical profile of meteorological variables. Insects within the layers are frequently orientated, either downwind or at an angle to the wind, but the mechanisms involved in both layer formation and common orientation have remained elusive. Here, we show through the results of numerical simulations that if insects are treated as neutrally buoyant particles, they tend to be advected by vertical gusts (through the ‘turbophoretic’ mechanism) into layers in the atmosphere where the turbulent kinetic energy has local minima. These locations typically coincide with local maxima in the wind speed and/or air temperature, and they may also provide cues for orientation. However, the degree of layering predicted by this model is very much weaker than that observed in the field. We have therefore hypothesized that insects behave in a way that amplifies the turbophoretic effect by initiating climbs or descents in response to vertical gusts. New simulations incorporating this behaviour demonstrated the formation of layers that closely mimic field observations, both in the degree of concentration in layers and the rate at which they form

Donor and acceptor characteristics of native point defects in GaN

The semiconducting behaviour and optoelectronic response of gallium nitride is governed by point defect processes, which, despite many years of research, remain poorly understood. The key difficulty in the description of the dominant charged defects is determining a consistent position of the corresponding defect levels, which is difficult to derive using standard supercell calculations. In a complementary approach, we take advantage of the embedded cluster methodology that provides direct access to a common zero of the electrostatic potential for all point defects in all charge states. Charged defects polarise a host dielectric material with long-range forces that strongly affect the outcome of defect simulations; to account for the polarisation, we couple embedding with the hybrid quantum mechanical/molecular mechanical approach and investigate the structure, formation and ionisation energies, and equilibrium concentrations of native point defects in wurtzite GaN at a chemically accurate hybrid-density-functional-theory level. N vacancies are the most thermodynamically favourable native defects in GaN, which contribute to the n-type character of as-grown GaN but are not the main source, a result that is consistent with experiment. Our calculations show no native point defects can form thermodynamically stable acceptor states. GaN can be easily doped n-type, but, in equilibrium conditions at moderate temperatures acceptor dopants will be compensated by N vacancies and no significant hole concentrations will be observed, indicating non-equilibrium processes must dominate in p-type GaN. We identify spectroscopic signatures of native defects in the infrared, visible and ultraviolet luminescence ranges and complementary spectroscopies. Crucially, we calculate the effective-mass-like-state levels associated with electrons and holes bound in diffuse orbitals. These levels may be accessible in competition with more strongly-localised states in luminescence processes and allow the attribution of the observed 3.46 and 3.27 eV UV peaks in a broad range of GaN samples to the presence of N vacancies