Hybrid Density Functional Theory Calculations Research Articles

Electronic properties of corundum-like Ir2O3 and Ir2O3-Ga2O3 alloys

In the hexagonal, corundum-like structure, α-Ga2O3 has a bandgap of ∼ 5.1 eV, which, combined with its relatively small electron effective mass, high Baliga's figure of merit, and high breakdown field, makes it a promising candidate for power electronics. Ga2O3 is easy to dope n-type, but impossible to dope p-type, impeding the realization of some electronic device designs. Developing a lattice-matched p-type material that forms a high-quality heterojunction with n-type Ga2O3 would open new opportunities in electronics and perhaps optoelectronic devices. In this work, we studied Ir2O3 as a candidate for that purpose. Using hybrid density functional theory calculations we predict the electronic band structure of α-Ir2O3 and compare that to α-Ga2O3, and study the stability and electronic properties of α-(IrxGa1−x)2O3 alloys. We discuss the band offset between the two materials and compare it with recently available experimental data. We find that the Ir d bands that compose the top of the valence band in α-Ir2O3 are much higher in energy than O p bands in α-Ga2O3, possibly enabling effective p-type doping. Our results provide an insight into using the Ir2O3 or Ir2O3-Ga2O3 alloys as p-type material lattice-matched to α-Ga2O3 for the realization of p–n heterojunctions.

Transition-Metal-Related Quantum Emitters in Wurtzite AlN and GaN.

Transition-metal centers exhibit a paramagnetic ground state in wide-bandgap semiconductors and are promising for nanophotonics and quantum information processing. Specifically, there is a growing interest in discovering prominent paramagnetic spin defects that can be manipulated using optical methods. Here, we investigate the electronic structure and magneto-optical properties of Cr and Mn substitutional centers in wurtzite AlN and GaN. We use state-of-the-art hybrid density functional theory calculations to determine level structure, stability, optical signatures, and magnetic properties of these centers. The excitation energies are calculated using the constrained occupation approach and rigorously verified with the complete active space configuration interaction approach. Our simulations of the photoluminescence spectra indicate that in AlN and in GaN are responsible for the observed narrow quantum emission near 1.2 eV. We compute the zero-field splitting (ZFS) parameters and outline an optical spin polarization protocol for and . Our results demonstrate that these centers are promising candidates for spin qubits.

Training Machine-Learned Density Functionals on Band Gaps.

The systematic underestimation of band gaps is one of the most fundamental challenges in semilocal density functional theory (DFT). In addition to hindering the application of DFT to predicting electronic properties, the band gap problem is intimately related to self-interaction and delocalization errors, which make the study of charge transfer mechanisms with DFT difficult. To expand the range of available tools for addressing the band gap problem, we design an approach for machine learning density functionals based on Gaussian processes to explicitly fit single-particle energy levels. We also introduce nonlocal features of the density matrix that are expressive enough to fit these single-particle levels. Combining these developments, we train a machine-learned functional for the exact exchange energy that predicts molecular energy gaps and reaction energies of a wide range of molecules in excellent agreement with reference hybrid DFT calculations. In addition, while being trained solely on molecular data, our model predicts reasonable formation energies of polarons in solids, showcasing its transferability and robustness. We discuss how this approach can be generalized to full exchange-correlation functionals, thus paving the way to the design of state-of-the-art functionals for the prediction of electronic properties of molecules and materials.

Tuning the optoelectronic properties of graphene monoxide by electric field, strain and heterostructure with Cd[formula omitted] ([formula omitted]=S, Se or Te)

Hydrogen production via photocatalytic water splitting has become a promising technique for developing clean and sustainable energy system. Low-dimensional carbon-based materials are under focus to develop high efficiency visible-light photocatalysts. Among the various 2D graphene-based materials, graphene oxides (GO) attracted attention in recent years. Recently identified GO such as graphene monoxide (GMO) shows promising electronic structure characteristics such as direct band gap behavior, high optical absorption, and well-dispersed band edges to use them in higher efficiency optoelectronic applications. Nevertheless, its valence band edge is distant from the water oxidation potential, and band gap value exceeds the ideal band gap required to effectively harvest solar energy, which minimizes its practical application in photocatalytic water splitting. Here, using hybrid density functional theory calculations, we are exploring the effect of applied electric field/strain on the photocatalytic water splitting and photovoltaic properties of GMO. We found that even after applying an electric field or strain, GMO retains the desirable direct band gap behavior, well-dispersed bands at the band edges, and high optical absorption in the visible range. Further, the band alignment analysis suggests that the application of compressive strain enhances the efficiency of photocatalytic water splitting by straddling the band edges with water redox potentials. Additionally, we explored the optoelectronic properties of GMO by designing its heterostructure with CdS, CdSe, and CdTe monolayers. Remarkably, the studied heterostructures demonstrated superior optical absorption in the visible spectrum and a low recombination rate of charge carriers by separating them across different layers with type-II band alignment; suggesting that these heterostructures will be efficient candidates for visible energy photocatalytic water splitting and higher-efficiency solar cells.

Donor-induced electrically charged defect levels: examining the role of indium and n-type defect-complexes in germanium

Defect levels induced by defect-complexes in Ge play important roles in device fabrication, characterization, and processing. However, only a few defect levels induced by defect-complexes have been studied, hence limiting the knowledge of how to control the activities of numerous unknown defect-complexes in Ge. In this study, hybrid density functional theory calculations of defect-complexes involving oversize atom (indium) and n-type impurity atoms in Ge were performed. The formation energies, defect-complex stability, and electrical characteristics of induced defect levels in Ge were predicted. Under equilibrium conditions, the formation energy of the defect-complexes was predicted to be within the range of 5.90–11.38 eV. The defect-complexes formed by P and In atoms are the most stable defects with binding energy in the range of 3.31-3.33 eV. Defect levels acting as donors were induced in the band gap of the host Ge. Additionally, while shallow defect levels close to the conduction band were strongly induced by the interactions of Sb, P, and As interstitials with dopant (In), the double donors resulting from the interactions between P, As, N, and the host atoms including In atom are deep, leading to recombination centers. The results of this study could be applicable in device characterization, where the interaction of In atom and n-type impurities in Ge is essential. This report is important as it provides a theoretical understanding of the formation and control of donor-related defect-complexes in Ge.

Bi(III)‐based oxide semiconductors with ambipolar doping: (Na, K)BiO2

AbstractBi(III)‐based oxides are emerging as important semiconductors for future electronic applications. Through hybrid density functional theory calculations and defect analysis, we demonstrate that ABi(III)O2 (A = Na or K) is a promising wide‐band‐gap bipolar semiconductor. Our calculations predict ABiO2 to have a large band gap of 1.97 eV for NaBiO2 and 2.77 eV for KBiO2. Unlike widely‐used oxide semiconductors such as In2O3 and ZnO, the spatially extended cation states (Bi 6s) of ABiO2 significantly contribute to the valence band maximum, enhancing p‐type dopability. We indeed show that potential acceptors, such as SrBi, produce shallow levels. In addition, n‐type doping is found to be possible through the extrinsic doping of heterovalent elements such as Te and F. The band‐structure analysis reveals that ABiO2 has small effective masses for electrons and holes (< 1m0 where m0 is the electron rest mass), indicating favorable electron and hole transport properties.

Strain and Electric Field Engineering of G-ZnO/SnXY (X, Y = S, Se) S-Scheme Heterostructures for Photocatalyst and Electronic Device Applications: A Hybrid DFT Calculation.

Using hybrid density functional theory calculations, we systematically study the biaxial strain and electric field modulated electronic properties of g-ZnO/SnS2, g-ZnO/SnSe2, and g-ZnO/SnSSe S-scheme van der Waals heterostructures (vdWHs). g-ZnO/SnS2 and g-ZnO/SnSSe are found to be promising photocatalysts for water splitting with high solar-to-hydrogen efficiencies, even under acidic, alkaline, and high-stress conditions. The strain effect on the bandgaps of g-ZnO/SnXY is explained in detail according to the correlation between geometry structure and orbital hybridization of SnXY, which could help understand the strain-induced band structure evolutions in other SnXY (X, Y = S, Se)-based vdWHs. It is surprising that under an external electric field, g-ZnO/SnS2, g-ZnO/SnSe2, and g-ZnO/SnSSe can offer the occupied nearly free-electron (NFE) states. In many materials, NFE states are usually unoccupied and is not conducive to the charge transport. The NFE state in g-ZnO/SnSe2 is the most sensitive to the electric field and might be promising electron transport channel in nanoelectronic devices. g-ZnO/SnSe2 might also have application potential in gas sensors and high-temperature superconductors.

Hybrid Density Functional Theory Calculations for the Crystal Structure and Electronic Properties of Al3+ Doped KDP Crystals

Intentionally adding select ions such as Al3+ could be helpful in controlling the crystal habit of KDP crystal for high yield of optics. The study of how Al3+ ions affect crystal quality can provide a basis for selecting an appropriate doping level without negatively affecting the optical properties of crystals. Here, the influence of Al3+ ions on the crystal structure and properties of KDP crystals have been investigated by using first-principles calculations. Theoretical calculations show that Al3+ ions mainly replace K sites in KDP crystals and could complex with intrinsic VH− point defects to form AlK2+ + 2VH− cluster defects. The linear absorption spectra indicate that the presence of Al3+ ions has minimal impact on the linear absorption of KDP crystals, aligning well with the experimental findings. And Al3+ ions could cause a slight shortening of the band gap of KDP crystals. However, these ions could bring significant deformations of O-H bonds. As the concentration of Al3+ ions increase, more O-H bonds linking to PO4 groups are distorted in KDP crystals. As a result, the structural instability could be fast enhanced with increasing the defect concentration. Therefore, high concentrations of Al3+ ions could cause the instability of the crystal structure, which finally affects the laser-induced damage resistance of the KDP crystals. This manuscript contributes to a more comprehensive understanding of the physical mechanisms by which different impurity ions affect the optical properties of KDP crystals.

Hybrid density functional theory simulation of sodium impurity and impurity–vacancy defect complexes in germanium: perspectives of defect engineering for activation of shallow donors

At present, germanium (Ge) as a high-mobility material is considered as a possible replacement for Si in microelectronics. The main obstacle in the method is the large vacancy concentration obtained after the implantation of shallow donors. This prevents the formation of n+ regions and has a negative impact on device performance. One way to eliminate the detrimental effects of such defects is through the codoping approach. In this study, the behavior of Na impurities in germanium together with the formation of defect complexes with vacancies, divacancies and shallow donors (P and As) were investigated using hybrid density functional theory calculations. The site preference, diffusion barriers, charge states and binding energies of various complexes, as well as the activation of donor–vacancy complexes with both F and Na codoping were investigated. For this purpose, two extreme cases were considered. Firstly, we calculate the concentrations of substitutional and interstitial Na together with monovacancies in the case of quasi-equilibrium conditions realized for doping from melt. Another extreme case is Na codoping during ion implantation. Our calculations show that Na passivates vacancies, divacancies and donor–vacancy complexes (E-centers) with a large energy gain, which prevents rapid donor diffusion similar to the case of doping with fluorine. We have shown that the passivation of E-centers with both F and Na impurities leads to the back transformation of such complexes into shallow donors. This means that codoping with Na may neutralize the harmful effects of vacancies and is a perspective for defect engineering.

Comment on “High‐Efficient Blue Emission and Bandgap Engineering from Jahn‒Teller Distorted Halide Double Perovskites”

AbstractIn a recent publication, Liu et al. investigated the doping strategy of pentavalent antimony (Sb5+) in the benchmark material Cs2NaInCl6, achieving a bright blue emission with a high photoluminescence quantum yield of ≈90% at low doping concentrations and bandgaps as low as 1.24 eV at high doping concentrations (Adv. Opt. Mater. 2024, 12, 2301576). In this comment, by reanalyzing Liu et al.' data and conducting hybrid density functional theory calculations, the study provides evidence supporting the incorporation of Sb3+ ions rather than “Sb5+ ions”, as the cause of the efficient blue emission observed in the lightly‐doped Cs2NaInCl6 samples. Furthermore, it is proposed that the narrowing of the bandgap in the “heavily‐doped Cs2NaInCl6” samples is a result of the formation of a new phase related to a mixed‐valence salt, Cs4SbIIISbVCl12.

Probing the role of surface termination in the adsorption of azupyrene on copper.

The role of the inorganic substrate termination, within the organic-inorganic interface, has been well studied for systems that contain strong localised bonding. However, how varying the substrate termination affects coordination to delocalised electronic states, like that found in aromatic molecules, is an open question. Azupyrene, a non-alternant polycyclic aromatic hydrocarbon, is known to bind strongly to metal surfaces through its delocalised π orbitals, thus yielding an ideal probe into delocalised surface-adsorbate interactions. Normal incidence X-ray standing wave (NIXSW) measurements and density functional theory calculations are reported for the adsorption of azupyrene on the (111), (110) and (100) surface facets of copper to investigate the dependence of the adsorption structure on the substrate termination. Structural models based on hybrid density functional theory calculations with non-local many-body dispersion yield excellent agreement with the experimental NIXSW results. No statistically significant difference in the azupyrene adsorption height was observed between the (111) and (100) surfaces. On the Cu(110) surface, the molecule was found to adsorb 0.06 ± 0.04 Å closer to the substrate than on the other surface facets. The most energetically favoured adsorption site on each surface, as determined by DFT, is subtly different, but in each case involved a configuration where the aromatic rings were centred above a hollow site, consistent with previous reports for the adsorption of small aromatic molecules on metal surfaces.

Hybrid density functional theory calculations for surface damaged phosphate products of laser irradiated KDP crystals

Surface damage products cause more UV absorption and increase surface damage compared to KDP crystals.

Absorption spectra of the purple nonsulfur bacteria light-harvesting complex: A DFT study of the B800 part

We’ve studied the B800 part of Rhodoblastus acidophilus light-harvesting complex (LH2) by several quantum chemical techniques based on the density functional theory (DFT) and determined the specific method and a minimal reliable model suitable for further studies of the LH2. In addition to bacteriochlorophyll a molecules, the minimal model includes two α and one β chain amino acids. Within the model, we are able to reproduce the contribution of the B800 ring of nine bacteriochlorophyll a molecules to the near infrared Qy absorption band. We also discuss the use of hybrid DFT calculations for precise energy and optical estimations and DFT-based tight binding (DFTB) method for the large-scale calculations. Crucial importance of Hartree-Fock exchange interaction for the correct description of B800 peak position was shown.

Ground and excited state charge transfer at aqueous nanodiamonds.

Nanodiamonds (NDs) are unique carbonaceous materials with exceptionally high stability, hardness, and notable electronic properties. Their applications in photocatalysis, biomedicine, and energy materials are usually carried out in aqueous environments, where they interact with aqueous adsorbates. Especially, electron density may rearrange from the diamond material toward oxidative adsorbates such as oxygen, which is known as charge transfer doping. In this article, we quantify the charge transfer doping for NDs with inhomogeneous surface coverings (hydroxyl, fluorine, and amorphous carbon), as well as NDs doped with heteroatoms (B, Si, N) using hybrid density functional theory (DFT) calculations. The transfer doping magnitude is largely determined by the NDs' highest occupied molecular orbital energies, which can in turn be modified by the surface covering and doping. However, local modifications of the ND structures do not have any local effects on the magnitude of the charge transfer. We furthermore analyze the impact of aqueous adsorbates on the excited states of an aqueous ND in the context of photocatalysis via time-dependent DFT. Here, we find that the excited electrons are biased to move in the direction of the respective oxidative adsorbate. Surprisingly, we find that also unreactive species such as nitrous oxide may attract the excited electrons, which is probably due to the positive partial charge that is induced by the local N O solvation geometry.

How Axial Coordination Regulates the Electronic Structure and C-H Amination Reactivity of Fe-Porphyrin-Nitrene?

Detailed electronic structure and its correlation with the intramolecular C-H amination reactivity of Fe-porphyrin-nitrene intermediates bearing different "axial" coordination have been investigated using multiconfigurational complete active space self-consistent field (CASSCF), N-electron valence perturbation theory (NEVPT2), and hybrid density functional theory (DFT-B3LYP) calculations. Three types of "axial" coordination, -OMe/-O(H)Me (1-Sul/2-Sul), -SMe/-S(H)Me (3-Sul/4-Sul), and -NMeIm (MeIm = 3-methyl-imidazole) (5-Sul) mimicking serine, cysteine, and histidine, respectively, along with no axial coordination (6-Sul) have been considered to decipher how the "axial" coordination of different strengths regulates the electronic integrity of the Fe-N core and nitrene-transfer reactivity of Fe-porphyrin-nitrene intermediates. CASSCF-based natural orbitals reveal two distinct classes of electronic structures: Fe-nitrenes (1-Sul and 3-Sul) with relatively stronger axial coordination (-OMe and -SMe) display "imidyl" nature and those (2-Sul, 4-Sul, and 6-Sul) with weaker axial coordination (-O(H)Me, -S(H)Me and no axial coordination) exhibit "imido-like" character. A borderline between the two classes is also observed with NMeIm axial coordination (5-Sul). Axial coordination of different strengths not only regulates the electronic structure but also modulates the Fe-3d orbital energies, as revealed through the d-d transition energies obtained by CASSCF/NEVPT2 calculations. The relatively lower energy of Fe-3dz2 orbital allows easy access to low-lying high-spin quintet states in the cases of weaker "axial" coordination (2-Sul, 4-Sul, and 6-Sul), and the associated hydrogen atom transfer (HAT) reactivity appears to involve two-state triplet-quintet reactivity through minimum energy crossing point (3,5MECP) between the spin states. In stark contrast, Fe-nitrenes with relatively stronger "axial" coordination (1-Sul and 3-Sul) undergo triplet-only HAT reactivity. Overall, this in-depth electronic structure investigation and HAT reactivity evaluation reveal that the weaker axial coordination in Fe-porphyrin-nitrene complexes (2-Sul, 4-Sul, and 6-Sul) can promote more efficient C-H oxidation through the quintet spin state.

Point Defects in Silicon-Doped β-Ga2O3: Hybrid-DFT Calculations.

In this work, hybrid density functional theory calculations are used to evaluate the structural and electronic properties and formation energies of Si-doped β-Ga2O3. Overall, eight interstitial (Sii) and two substitutional (SiGa) positions are considered. In general, our results indicate that the formation energy of such systems is significantly influenced by the charge state of the defect. It is confirmed that it is energetically more favorable for the substitution process to proceed under Ga-poor growth conditions than under Ga-rich growth conditions. Furthermore, it is confirmed that the formation of SiGaI with a tetrahedral coordination geometry is more favorable than the formation of SiGaII with an octahedral one. Out of all considered interstitial positions, due to the negative formation energy of the Si +3 charge state at i8 and i9 interstitial positions over the wide range of Fermi energy, this type of defect can be spontaneously stable. Finally, due to a local distortion caused by the presence of the interstitial atom as well as its charge state, these systems obtain a spin-polarized ground state with a noticeable magnetic moment.

Jahn–Teller distortion in Sr2FeO4: group-theoretical analysis and hybrid DFT calculations

We present theoretical justification for distorted Ruddlesden–Popper (RP) phases of the first-order by using hybrid density functional theory (DFT) calculations and group-theoretical analysis. We, thus, demonstrate the existence of the Jahn–Teller effect around an Fe^{4texttt {+}} ion in Sr_{2}FeO_{4}. On the calculation side, we have established a combination of Wu–Cohen (WC) exchange and Perdew-Wang (PW) correlation in a three-parameter functional WC3PW, giving the most accurate description of Sr_{2}FeO_{4} from the comparison of three hybrid DFT functionals. Self-consistently obtained Hartree–Fock exact exchange of 0.16 demonstrates consistent results with the experimental literature data. Importantly, we explain conditions for co-existing proper and pseudo-Jahn–Teller effects from the crystalline orbitals, symmetry-mode analysis and irreps products. Moreover, phonon frequency calculations support and confirm the results of symmetry-mode analysis. In particular, the symmetry-mode analysis identifies a dominating irreducible representation of the Jahn-Teller mode (X2+) and corresponding space group (SG) of ground state structure (SG Cmce model). Therefore, the usually suggested high-symmetry tetragonal crystal structure (SG I4/mmm model) is higher in energy by 121 meV/f.u. (equivalent to the Jahn-Teller stabilization energy) compared with the distorted low-symmetry structure (SG Cmce model). We also present diffraction patterns for the two crystal symmetries to discuss the differences. Therefore, our results shed light on the existence of low-symmetry RP phases and make possible direct comparisons with future experiments.

Exploring spin states by hybrid functional methods to define correct trends in electrocatalytic activity of SACs embedded in N-doped graphene

Embedding transition metal atoms in graphene is a promising strategy to make it an effective electrocatalyst for the oxygen evolution (OER) and reduction (ORR) reactions, which are crucial processes for the success of the energy transition. In this regard, theoretical investigations can be valuable complementary tools to experimental work, but only if they are able to adequately describe the system under examination. Transition metal atoms trapped in graphene pose serious challenges due to the presence of strongly correlated d-electrons, which can lead to complex spin configurations to be explored. In this work, by hybrid density functional theory (DFT) calculations we investigated several first-row transition metal atoms embedded in N-doped graphene as potential electrocatalysts for the OER and ORR. A detailed spin-dependent search has been performed to define the lowest energy spin state configurations for all intermediates along the associative path, finding Ni and Fe as the most promising systems for the OER and ORR, based on overpotential values (η) of 0.58 V and 0.52 V, respectively. Interestingly, if the study is limited to low-spin configurations, the resulting overpotential values differ within the range of 0.5 V, changing the order of activity between the various electrocatalytic systems. The most striking case is that of Fe, where according to the low-spin state reaction path it would suggest this to be the worst electrocatalyst for ORR. Thus, this work conveys a very important message and general warning to the community on trusting only data that come from a full spin optimization.

Effect of Magnesium Substitution on Structural Features and Properties of Hydroxyapatite.

Hydroxyapatite (HAP) is the main mineral component of bones and teeth. It is widely used in medicine as a bone filler and coating for implants to promote new bone growth. Ion substitutions into the HAP structure highly affect its properties. One of the most important substituents is magnesium. This paper presents new results obtained using high-precision hybrid density functional theory calculations for Mg/Ca substitutions in HAP in a wide magnesium concentration range within a 2 × 2 × 2 supercell model. Experimental data on the mechanochemical synthesis of HAP-Mg samples with different Mg concentrations are also presented. A comparison between the experiment and the theory showed good agreement: the HAP-Mg unit cell parameters and volume decreased with increasing degree of Mg/Ca substitution. The changes in the distances between the Ca and O, Ca and H, and Mg and O ions upon Mg/Ca substitution in different calcium positions was analyzed. The resulting asymmetry and distortion of the cell parameters were evaluated. It was shown that bulk modulus, energy levels, and band gap depend on the degree of Mg substitutions in the Ca1 and Ca2 positions. The formation energies of Mg/Ca substitutions showed non-monotonic behavior that was different for Ca1 and Ca2 positions. The Ca2 position had a slightly higher probability (~5 meV/f.u.) of substitution than Ca1 position at a Mg concentration x = 0.5. At x = 1, substitution in both positions can coexist. The simulated IR spectra for different Mg/Ca substitutions showed that Mg in the Ca2 position changes the IR spectrum more significantly than Mg in the Ca1 position. Similar changes were recorded in the IR spectra of the synthesized samples. The electronic structure is shown to be sensitive to the number and position of substitutions, which may be used to tweak the optical properties of the HAP-Mg material.

Even Faster Exact Exchange for Solids via Tensor Hypercontraction.

Hybrid density functional theory (DFT) remains intractable for large periodic systems due to the demanding computational cost of exact exchange. We apply the tensor hypercontraction (THC) (or interpolative separable density fitting) approximation to periodic hybrid DFT calculations with Gaussian-type orbitals using the Gaussian plane wave approach. This is done to lower the computational scaling with respect to the number of basis functions (N) and k-points (Nk) at a fixed system size. Additionally, we propose an algorithm to fit only occupied orbital products via THC (i.e., a set of points, NISDF) to further reduce computation time and memory usage. This algorithm has linear scaling cost with k-points, no explicit dependence of NISDF on basis set size, and overall cubic scaling with unit cell size. Significant speedups and reduced memory usage may be obtained for moderately sized k-point meshes, with additional gains for large k-point meshes. Adequate accuracy can be obtained using THC-oo-K for self-consistent calculations. We perform illustrative hybrid density function theory calculations on the benzene crystal in the basis set and thermodynamic limits to highlight the utility of this algorithm.