Hybrid DFT calculations of the atomic and electronic structure for ABO3 perovskite (001) surfaces

Abstract We present the results of first-principles calculations on two possible terminations of the (0 0 1) surfaces of SrTiO3, BaTiO3, and PbTiO3 perovskite crystals. Atomic structure and the electronic configurations were calculated for different 2D slabs, both stoichiometric and non-stoichiometric, using hybrid (B3PW) exchange-correlation technique and re-optimized basis sets of atomic (Gaussian) orbitals. Results are compared with previous calculations and available experimental data. The electronic density distribution near the surface and covalency effects are discussed in details for all three perovskites. Both SrTiO3 and BaTiO3 (0 0 1) surfaces demonstrate reduction of the optical …

Electronic and optical properties of pristine, N- and S-doped water-covered TiO2 nanotube surfaces

For rational design and improvement of electronic and optical properties of water-splitting photocatalysts, the ability to control the band edge positions relative to the water redox potentials and the photoresponse as a function of environmental conditions is essential. We combine ab initio molecular dynamics simulations with ab initio many-body theoretical calculations to predict the bandgap and band edge energies, as well as the absorption spectrum of pristine and N- and S-doped TiO2 nanotubes using the DFT+U and G0W0 approaches. Both levels of theory show similar trends, and N+S-codoping appears to be the optimal system for photocatalytic water splitting both in dry and humid conditions…

Titania nanotubes modeled from 3- and 6-layered (101) anatase sheets: Line group symmetry and comparative ab initio LCAO calculations

Abstract The formalism of line groups for one-periodic (1D) nanostructures with rotohelical symmetry has been applied for construction of TiO 2 nanotubes (NTs). They are formed by rolling up the stoichiometric two-periodic (2D) sheets cut from the energetically stable (1 0 1) anatase surface, which contains either six (O–Ti–O_O–Ti–O) or three (O–Ti–O) layers. After optimization of geometry the former keeps the centered rectangular symmetry of initial slab while the latter is spontaneously reconstructed to the hexagonal fluorite-type (1 1 1) sheet. We have considered the four sets of TiO 2 NTs with optimized 6- and 3-layered structures, which possess the two pairs of either anatase (− n , n …

First principles evaluation on photocatalytic suitability of 2H structured and [0001] oriented WS2 nanosheets and nanotubes

This study was supported by the EC ERA.Net RUS Plus Project No. 237 WATERSPLIT. R.E. acknowledges the financial support provided by the Russian Foundation for Basic Research (grant N 17-03-00130a) and High Performance Computer Center of St. Petersburg University for the assistance. The authors are indebted to D. Bocharov, O. Lisovski and E. Spohr for stimulating discussions.

First-Principles Evaluation of the Morphology of WS2 Nanotubes for Application as Visible-Light-Driven Water-Splitting Photocatalysts

This study was supported by the EC ERA.Net RUS Plus project No. 237 WATERSPLIT as well as Russian Basic Research Foundation No. 16-53-76019. S.K. and E.S. furthermore gratefully acknowledge computing time granted by the Center for Computational Sciences and Simulation (CCSS) of the Universitaẗ Duisburg-Essen and the supercomputer magnitUDE (DFG grants INST 20876/209-1 FUGG, INST 20876/243-1 FUGG) provided by the Zentrum für Informations-und Mediendienste (ZIM). E.S. is also grateful for support by the Cluster of Excellence RESOLV (EXC1069) funded by the Deutsche Forschungsgemeinschaft.

Positron Annihilation Lifetime Spectroscopy Insight on Free Volume Conversion of Nanostructured MgAl2O4 Ceramics

H.K. and A.I.P. are grateful for the support from the COST Action CA17126. H.K. was also supported by the Ministry of Education and Science of Ukraine (project for young researchers No. 0119U100435). In addition, I.K. and H.K. were also supported by the National Research Foundation of Ukraine via project 2020.02/0217, while the research of A.I.P. was funded by the Latvian research council via the Latvian National Research Program under the topic ?High-Energy Physics and Accelerator Technologies?, Agreement No: VPP-IZM-CERN-2020/1-0002. In addition, the research of A.I.P. has been supported by the Latvian-Ukrainian Grant LV-UA/2021/5. The Institute of Solid State Physics, University of Latvi…

Electronic charge redistribution in LaAlO$_3$(001) thin films deposited at SrTiO$_3$(001) substrate: First principles analysis and the role of stoichiometry

We present a comprehensive first-principles study of the electronic charge redistribution in atomically sharp LaAlO$_3$/SrTiO$_3$(001) heterointerfaces of both n- and p-types allowing for non-stoichiometric composition. Using two different computational methods within the framework of the density functional theory (linear combination of atomic orbitals and plane waves) we demonstrate that conducting properties of LaAlO$_3$/SrTiO$_3$(001) heterointerfaces strongly depend on termination of LaAlO$_3$ (001) surface. We argue that both the polar "catastrophe" and the polar distortion scenarios may be realized depending on the interface stoichiometry. Our calculations predict that heterointerface…

Ab initio modelling of the effects of varying Zr (Ti) concentrations on the atomic and electronic properties of stoichiometric PZT solid solutions

Abstract Lead zirconate titanate Pb(ZrxTi1−x)O3 solid solution is considered as one of the most advanced ferroelectric and piezoelectric materials. Consequent variation of Zr (Ti) concentrations significantly affects the atomic and electronic properties of PZT structures. To perform ab initio modelling of different morphologies for lead zirconate titanate, we are using approach of hybrid density functional B3PW as implemented in CRYSTAL14 computer code. In this study, we are performing large-scale calculations of such PZT parameters as optimized lattice constants, atomic charges and bond populations, as well as band structure (e.g., band gap) and density of states.

First principles hybrid DFT calculations of BaTiO3/SrTiO3(001) interface

Abstract We present a first-principles study of BaTiO 3 /SrTiO 3 (001) interfaces taking into account non-stoichiometric compositions. By means of hybrid exchange–correlation functional within density functional theory (DFT) we demonstrate that charge redistribution in the interface region weakly affects the electronic structure of studied material, while change in the stoichiometry (termination of deposited BaTiO 3 (001) thin film) yields in significant shifts of band edges. The optical band gap of BaTiO 3 /SrTiO 3 (001) interface depends mostly on BaO or TiO 2 termination of the upper layer. Based on results of our calculations we predict enhancement of the Ti–O chemical bond covalency ne…

First-principles calculations of point defects in inorganic nanotubes

The first-principles calculations have been performed to investigate the ground-state properties of monoperiodic boron nitride (BN), TiO2, and SrTiO3 single-walled nanotubes (SW NTs) containing extrinsic point defects. The hybrid exchange–correlation functionals PBE, B3LYP, and B3PW within the framework of density functional theory (DFT) have been applied for large-scale ab initio calculations on NTs with the following substitutional impurities: AlB, PN, GaB, AsN, InB, and SbN in the BN NT, as well as CO, NO, SO, and FeTi in the TiO2 and SrTiO3 NTs, respectively. The variations in formation energies obtained for equilibrium defective nanostructures allow us to predict the most stable compos…

The Effect of Oxygen Vacancies on the Atomic and Electronic Structure of Cubic ABO3Perovskite Bulk and the (001) Surface:Abinitio Calculations

We employed the hybrid DFT-LCAO and GGA-PW approaches as implemented in the CRYSTAL and VASP codes, respectively, for large supercell calculations of neutral O vacancies with trapped electrons (known as F centers) in the bulk and on the (001) surface of three cubic perovskite crystals (SrTiO 3 , PbTiO 3 , and PbZrO 3 ). The local lattice relaxation, charge redistribution, and positions of defect energy levels within the band gap are compared for three perovskites under study. We demonstrate how the difference in chemical composition of host materials leads to quite different defect properties.

First Principles Calculations of Atomic and Electronic Structure of TiAl3+- and TiAl2+-Doped YAlO3

In this paper, the density functional theory accompanied with linear combination of atomic orbitals (LCAO) method is applied to study the atomic and electronic structure of the Ti3+ and Ti2+ ions substituted for the host Al atom in orthorhombic Pbnm bulk YAlO3 crystals. The disordered crystalline structure of YAlO3 was modelled in a large supercell containing 160 atoms, allowing simulation of a substitutional dopant with a concentration of about 3%. In the case of the Ti2+-doped YAlO3, compensated F-center (oxygen vacancy with two trapped electrons) is inserted close to the Ti to make the unit cell neutral. Changes of the interatomic distances and angles between the chemical bonds in the de…

Formation of linear Ni nanochains inside carbon nanotubes: Prediction from density functional theory

Abstract First principles calculations have been performed to investigate the ground state properties of monoperiodic single-walled carbon nanotubes (CNTs) containing nanochain of aligned Ni atoms inside. Using the PBE exchange-correlation functional ( E xc ) within the framework of density functional theory (DFT) we predict the clusterization of Ni filaments in ( n ,0) CNTs for n ⩾  9 and for ( n , n ) CNTs for n ⩾  6. The variations in formation energies obtained for equilibrium defective nanostructures allow us to predict the most stable Ni@CNT compositions. Finally, the electronic charge redistribution has been calculated in order to explore intermolecular properties leading to stronger…

Electronic Properties of Layered Ba0.5Sr0.5TiO3 Heterostructure: Ab initio Hybrid Density Functional Calculations

Ab initio calculations of the BST heterostructure with equiatomic constituent of Sr and Ba species has been carried out within hybrid functional B3PW involving a hybrid of non-local Fock exchange and Becke's gradient corrected exchange functional combined with the non-local gradient corrected correlation potential by Perdew and Wang. The suggested scheme of calculations reproduces experimental lattice parameters of both pure BaTiO3 and SrTiO3. The calculated optical band gap for the pure SrTiO3 (BaTiO3) is 3.56 (3.46) eV (expt. 3.25 and 3.20 eV, respectively), i.e. agreement is much better than in the standard LDA or HF calculations. In the Ba0.5Sr0.5TiO3 solid solution the gap is reduced b…

First-principles calculations of the atomic and electronic structure ofFcenters in the bulk and on the (001) surface ofSrTiO3

The atomic and electronic structure, formation energy, and the energy barriers for migration have been calculated for the neutral O vacancy point defect F center in cubic SrTiO3 employing various implementations of density functional theory DFT. Both bulk and TiO2-terminated 001 surface F centers have been considered. Supercells of different shapes containing up to 320 atoms have been employed. The limit of an isolated single oxygen vacancy in the bulk corresponds to a 270-atom supercell, in contrast to commonly used supercells containing 40– 80 atoms. Calculations carried out with the hybrid B3PW functional show that the F center level approaches the conduction band bottom to within 0.5 eV…

Water Adsorption on Clean and Defective Anatase TiO2 (001) Nanotube Surfaces: A Surface Science Approach

We use ab initio molecular dynamics simulations to study the adsorption of thin water films with 1 and 2 ML coverage on anatase TiO2 (001) nanotubes. The nanotubes are modeled as 2D slabs, which consist of partially constrained and partially relaxed structural motifs from nanotubes. The effect of anion doping on the adsorption is investigated by substituting O atoms with N and S impurities on the nanotube slab surface. Due to strain-induced curvature effects, water adsorbs molecularly on defect-free surfaces via weak bonds on Ti sites and H bonds to surface oxygens. While the introduction of an S atom weakens the interaction of the surface with water, which adsorbs molecularly, the presence…

First Principles Calculations of Atomic and Electronic Structure of Ti3+Al- and Ti2+Al-Doped YAlO3

M.G.B. appreciates support from the Chongqing Recruitment Program for 100 Overseas Innovative Talents (grant no. 2015013), the Program for the Foreign Experts (grant no. W2017011), Wenfeng High-end Talents Project (grant no. W2016-01) offered by the Chongqing University of Posts and Telecommunications (CQUPT), Estonian Research Council grant PUT PRG111, European Regional Development Fund (TK141), and NCN project 2018/31/B/ST4/00924. This study was supported by a grant from Latvian Research Council No. LZP-2018/1-0214 (for AIP). Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Program H202…

Synthesis and characterization of GaN/ReS2, ZnS/ReS2 and ZnO/ReS2 core/shell nanowire heterostructures

This research was funded by the ERDF project “Smart Metal Oxide Nanocoatings and HIPIMS Technology”, project number: 1.1.1.1/18/A/073. Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART².

The electronic properties of an oxygen vacancy at ZrO2-terminated (001) surfaces of a cubic PbZrO3: computer simulations from the first principles

Combining B3PW hybrid exchange-correlation functional within the density functional theory (DFT) and a supercell model, we calculated from the first principles the electronic structure of both ideal PbZrO(3) (001) surface (with ZrO(2)- and PbO-terminations) and a neutral oxygen vacancy also called the F center. The atomic relaxation and electronic density redistributions are discussed. Thermodynamic analysis of pure surfaces indicates that ZrO(2) termination is energetically more favorable than PbO-termination. The O vacancy on the ZrO(2)-surface attracts approximately 0.3 e (0.7 e in the bulk PbZrO(3)), while the remaining electron density from the missing O(2-) ion is localized mostly on …

Comparative quantum chemistry study of the F-center in lanthanum trifluoride

Abstract In this study we report the results of first principle quantum chemical modeling of electronic structure and spatial configuration of LaF3 crystal containing the F-center. Theoretical predictions of atomic and electronic properties of LaF3 are given by means of density functional theory. From our modeling we predict that the F-center placed at fluorine ion position between the lanthanum planes at tysonite LaF3 is the most energetically stable. In order to interpret the structure of the optical absorption spectrum of X-irradiated LaF3 we performed calculations of excited and transition states of the F-center within the embedded cluster formalism using time dependent density function…

Electronic structure and thermodynamic stability of double-layeredSrTiO3(001)surfaces:Ab initiosimulations

Using the B3PW hybrid exchange-correlation functional within density-functional theory and employing Gaussian-type basis sets, we calculated the atomic and electronic structures and thermodynamic stability of three double-layered (DL) SrTiO3(001) surfaces: (i) SrO-terminated, (ii) TiO2-terminated, and (iii) (2×1) reconstruction of TiO2-terminated SrTiO3(001) recently suggested by Erdman et al. [Nature (London) 419, 55 (2002)]. A thermodynamic stability diagram obtained from first-principles calculations shows that regular TiO2- and SrO-terminated surfaces are the most stable. The stability regions of (2×1) DL TiO2- and DL SrO-terminated surfaces lie beyond the precipitation lines of SrO and…

First principles modeling of 3d-metal doped three-layer fluorite-structured TiO2 (4,4) nanotube to be used for photocatalytic hydrogen production

This study has been supported by the EC ERA.Net RUS Plus project No. 237 WATERSPLIT, Russian Basic Research Foundation No. 16-53-76019, and additionally by the IMIS2 Program (Latvia). The authors are also indebted to R. A. Evarestov and O. Lisovski for stimulating discussions as well as to A. Chesnokov for technical assistance.

Unexpected Epitaxial Growth of a Few WS2 Layers on {11̅00} Facets of ZnO Nanowires

Core–shell nanowires are an interesting and perspective class of radially heterostructured nanomaterials where epitaxial growth of the shell can be realized even at noticeable core–shell lattice mismatch. In this study epitaxial hexagonally shaped shell consisting of WS2 nanolayers was grown on {1100} facets of prismatic wurtzite-structured [0001]-oriented ZnO nanowires for the first time. A synthesis was performed by annealing in a sulfur atmosphere of ZnO/WO3 core–shell structures, produced by reactive dc magnetron sputtering of an amorphous a-WO3 layer on top of ZnO nanowire array. The morphology and phase composition of synthesized ZnO/WS2 core–shell nanowires were confirmed by scanning…

First principles calculations of SrZrO3 bulk and ZrO2-terminated (001) surface F centers

Abstract Using a supercell model and B3PW hybrid exchange-correlation functional in the framework of the density functional theory (DFT), as it is implemented in the CRYSTAL computer code, we performed ab initio calculations for the F -center located in the SrZrO 3 bulk and on the ZrO 2 -terminated (001) surface. According to the results of performed relaxation of atoms around the defect, two nearest Zr and four Sr atoms are repulsed, but all oxygen atoms are attracted towards both, the bulk and (001) surface F -center. The displacement magnitudes of atoms surrounding the bulk F -center are smaller than around the (001) surface F -center. The B3PW calculated SrZrO 3 bulk optical band gap (5…

Ab initio calculations of the atomic and electronic structure of layered Ba0.5Sr0.5TiO3 structures

Abstract Understanding of the atomic and electronic structure of Ba c Sr 1 −  c TiO 3 (BST) solid solutions is important for several applications including the non-volatile ferroelectric memories (dynamic random access memory, DRAM). We present results of ab initio calculations of several spatial arrangements of Ba 0.5 Sr 0.5 TiO 3 solid solutions based on DFT-HF B3PW hybrid method. We calculate the atomic and electronic structure, the effective charges, interatomic bond populations, the electronic density distribution, and densities of states for three layered structures with the same composition. The suggested method reproduces experimental lattice parameters of both pure BaTiO 3 and SrTi…

Hybrid DFT calculations of theFcenters in cubic ABO3perovskites

We employed the hybrid DFT-LCAO approach as implemented in the CRYSTAL code for 135 atom supercell calculations of O vacancies with trapped electrons (known as the F centers) in three cubic perovskite crystals: SrTiO3, PbTiO3 and PbZrO3. The local lattice relaxation, charge redistribution and defect energy levels in the optical gap are compared. We demonstrate how difference in a chemical composition of host materials leads to quite different defect properties.

Time-Dependent Density Functional Theory Calculations of N- and S-Doped TiO2 Nanotube for Water-Splitting Applications

This research was funded by the Latvian Council of Science grant LZP-2018/2-0083. Institute of Solid State Physics, University of Latvia, as the Center of Excellence, has received funding from the European Union?s Horizon 2020 Framework Program H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under Grant Agreement No. 739508, project CAMART2.

C-, N-, S-, and Fe-Doped TiO2 and SrTiO3 Nanotubes for Visible-Light-Driven Photocatalytic Water Splitting: Prediction from First Principles

The ground state electronic structure and the formation energies of both TiO2 and SrTiO3 nanotubes (NTs) containing CO, NO, SO, and FeTi substitutional impurities are studied using first-principles calculations. We observe that N and S dopants in TiO2 NTs lead to an enhancement of their visible-light-driven photocatalytic response, thereby increasing their ability to split H2O molecules. The differences between the highest occupied and lowest unoccupied impurity levels inside the band gap (HOIL and LUIL, respectively) are reduced in these defective nanotubes down to 2.4 and 2.5 eV for N and S doping, respectively. The band gap of an NO+SO codoped titania nanotube is narrowed down to 2.2 eV …

First-principles calculations on Fe-Pt nanoclusters of various morphologies

Financial support provided by Scientific Research Project for Students and Young Researchers Nr. SJZ/2016/17 implemented at the Institute of Solid State Physics, University of Latvia, is greatly acknowledged. A.P. and R.E. express their gratitude to High-performance computer centers of ISSP (University of Latvia) and St. Petersburg University. This research was partially supported by Graphene Flagship GrapheneCore1-AMD-696656-4.

Charged oxygen interstitials in corundum: first principles simulations

Combining supercell models and hybrid B3PW exchange-correlation functionals, ab initio simulations on quasi-stable configurations of interstitial ions in α-Al2O3 (corundum) crystals and possible migration trajectories have been modelled. We have studied crystalline distortion around migrating including interatomic distances and the effective atomic charges, as well as redistributions of the electronic density. Unlike neutral interstitial atom Oi studied by us previously, migrating ion does not form dumbbells with the nearest regular oxygen ions, due to the strong Coulomb interaction with the nearest cations as well as stronger repulsion between and adjacent regular ions. We have also estima…

Quantum chemical simulations of doped ZnO nanowires for photocatalytic hydrogen generation

Zinc oxide (ZnO) is considered in general as a promising material for solar water splitting. Its wurtzite-structured bulk samples, however, can be considered as active for photocatalytic applications only under UV irradiation, where they possess ∼1% efficiency of sunlight energy conversion due to their wide band gap (3.4 eV). Although pristine ZnO nanowires (NWs) possess noticeably narrower band gaps than the bulk, the tendency of band gap reduction with increasing NW diameter is insufficient, and further modification is required. We have contributed to filling this gap by performing a series of ab initio calculations on ZnO NWs of different diameters (dNW), which are mono-doped by metal (A…

Excited States Calculations of MoS2@ZnO and WS2@ZnO Two-Dimensional Nanocomposites for Water-Splitting Applications

This research was funded by the Latvian Scientific Council grant LZP-2018/2-0083. Institute of Solid State Physics, University of Latvia, as the Center of Excellence, has received funding from the European Union's Horizon 2020 Framework Program H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under Grant Agreement No. 739508, project CAMART2.

Comparative Theoretical Analysis of BN Nanotubes Doped with Al, P, Ga, As, In, and Sb

SUMMARY AND CONCLUDING REMARKS We have performed large-scale first-principles calculations ofthe electronic structure of (5,5) boron nitride nanotubescontaining the following substitutional impurity atoms: Al, P,Ga, As, In, and Sb. Calculations have been performed using thetwo methods: (i) linear combination of atomic orbitals(LCAO) with the atomic-centered Gaussian-type functions asa basis set and (ii) linearized augmented cylindrical wave(LACW) accompanied with the local density functional andmuffin-tin approximations for the electronic potential. In arelatively good qualitative agreement, both methods predict lowformation energies and, thus, relative stability of point defectsthat are assoc…

Ab initio calculations of the electronic structure for Mn2+-doped YAlO3 crystals

The electronic structure of Mn2+ ion substituted for the host Y atom in orthorhombic bulk YAlO3 crystals has been calculated by means of hybrid exchange-correlation functional HSE within density functional theory. The supercell approach has been used to simulate in Pbnm YAlO3 crystal the point defects, Mn-dopant and compensated the F+ center (oxygen vacancy with one trapped electron), to make unit cell neutral. Large 2 × 2 × 2 supercells of 160 atoms allow us to simulate substitutional point defect with concentration of about 3%. Mn2+ ions substituting for host Y form covalent Mn–O bonds, in opposite to the mostly ionic Y–O bond. The F center inserted to compensate the Mn2+ dopant in YAlO3 …

First-principles modeling of oxygen interaction with SrTiO3(001) surface: Comparative density-functional LCAO and plane-wave study

Large scale first-principles calculations based on density functional theory (DFT) employing two different methods (atomic orbitals and plane wave basis sets) were used to study the energetics, geometry, the electronic charge redistribution and migration for adsorbed atomic and molecular oxygen on defect-free SrTiO3(001) surfaces (both SrO- and TiO2-terminated), which serves as a prototype for many ABO3-type perovskites. Both methods predict substantial binding energies for atomic O adsorption at the bridge position between the oxygen surface ions and an adjacent metal ion. A strong chemisorption is caused by formation of a surface molecular peroxide ion. In contrast, the neutral molecular …

Back Cover: First-principles calculations of point defects in inorganic nanotubes (Phys. Status Solidi B 4/2013)

Ab initio modeling of copper adhesion on regular BaTiO3(001) surfaces

Ab initio calculations have been performed for copper adsorption on a regular, defect-free TiO"2- and BaO-terminated (001) surfaces of a cubic BaTiO"3, using a posteriori HF-CC method as implemented into the CRYSTAL-03 computer code. To clarify the nature of the interfacial bonding, we use slab models of the Cu/BaTiO"3(001) interfaces with different one-side substrate coverages, varied from 1/8 monolayer (ML) up to 1/2 ML, over both TiO"2- and BaO-terminated surfaces. TiO"2 termination has been found to be energetically more favorable for the adsorption of copper atoms. In agreement with previous experimental and theoretical data, our calculations indicate essential contribution of atomic p…

Oxygen adsorption atLa1−xSrxMnO3(001) surfaces: Predictions from first principles

Atomic and electronic structure of both perfect and nanostructured Ni(111) surfaces: First-principles calculations

article i nfo In this study, we perform first principles simulations on both atomically smooth and nanostructured Ni(111) slabs. The latter contains periodically distributed nickel nanoclusters atop a thin metal film gradually growing from adatoms and serving as a promising catalyst. Applying the generalized gradient approximation within the formalism of the density functional theory we compare the atomic and electronic structures of Ni bulk, as well as both perfect and nanostructured (111) surfaces obtained using two different ab initio approaches: (i) the linear combination of atomic orbitals and (ii) the projector augmented plane waves. The most essential inter-atomic forces between the …

DFT modelling of oxygen adsorption on the Ag-doped LaMnO3 (001) surface

This study was partly financed by the State Education Development Agency of the Republic of Latvia via the Latvian State Scholarship (A.A.) and Latvia-Ukraine Project (Grant LV-UA/2018/2 to E.K.). The work of T.I. is performed under the state assignment of IGM SB RAS. Also, this research was partly supported by the Ministry of Education and Science of the Republic of Kazakhstan in the framework of the scientific and technology Program BR05236795 ‘‘Development of Hydrogen Energy Technologies in the Republic of Kazakhstan’’. The authors thank M. Sokolov for technical assistance and valuable suggestions.

AB Initio Calculations of CUN@Graphene (0001) Nanostructures for Electrocatalytic Applications

Funding from European Union’s Horizon 2020 Research and Innovation Programme project under grant agreement No. 768789 is greatly acknowledged.

Electronic structure of MnAl3+- and MnAl2+-doped YAlO3: Prediction from the first principles

Abstract The atomic structure and electronic properties of Mn3+ and Mn2+ ions substituted for the host Al at YAlO3 have been studied from the first principles. The 2 × 2 × 2 supercell adopted for the bulk crystal phase of P b n m symmetry allows us to simulate substitutional point defect with concentration of about 3%. To perform ab initio modeling of Mn-doped YAlO3 we were using approach of hybrid exchange-correlation functional HSE within density functional theory. We predict a decrease of the Mn O bond covalency in the doped crystal with respect to the Al O bond of ideal orthorhombic YAlO3. Relatively large displacement of Y and Al atoms nearest to the F 0 -center inserted to stabilize t…

CNT Arrays Grown upon Catalytic Nickel Particles as Applied in the Nanoelectronic Devices: Ab Initio Simulation of Growth Mechanism

Carbon nanotubes, due to their exceptional and unique properties, have aroused a lot of research interest making them promising candidates as interconnects for future high-speed nanoelectronics. To predict a growth mechanism for carbon nanotubes (CNTs) upon a metal particle as synthesized in the porous membrane block then incorporated in the nanoelectronic device, we have performed a series of large-scale DFT-LCAO calculations using the CRYSTAL-06 code. Carbon adatoms can appear upon the densely-packed Ni(111) catalyst surface due to dissociation of hydrocarbon molecules (e.g., CH4) when applying the CVD method for the nanotube growth. We have started with adsorption properties of carbon at…

Theoretical and Experimental Studies of Charge Ordering in CaFeO 3 and SrFeO 3 Crystals

Influence of Au, Ag, and Cu Adatoms on Optical Properties of TiO2 (110) Surface: Predictions from RT-TDDFT Calculations

This study was financially supported by Flag-ERA JTC To2Dox project (S.P.) and M-ERA-NET2 project SunToChem (E.A.K.). M.G.B. thanks the support from the Program for the Foreign Experts (Grant No. W2017011) offered by Chongqing University of Posts and Telecommunications and the National Foreign Experts Program for “Belt and Road Initiative” Innovative Talent Exchange (Grant No. DL2021035001L), Estonian Research Council grant PUT PRG111, European Regional Development Fund (TK141), NCN project 2018/31/B/ST4/00924. Institute of Solid State Physics, University of Latvia, as the Center of Excellence, has received funding from the European Union’s Horizon 2020 Framework Program H2020-WIDESPREAD-01…

Symmetry and Models of Double-Wall BN and TiO2 Nanotubes with Hexagonal Morphology

The line symmetry groups for one-periodic (1D) nanostructures with rotohelical symmetry have been applied for symmetry analysis of double-wall boron nitride and titania nano- tubes (DW BN and TiO2 NTs) formed by rolling up the stoichiometric two-periodic (2D) slabs of hexagonal structure with the same or opposite orientation of translation and chiral vectors. We have considered the two sets of commensurate DW BN and TiO2 NTs with either armchair- or zigzag-type chiralities, i.e., (n1,n1)@(n2,n2 )o r (n1,0)@(n2,0), respectively. To establish theequilibriuminterwalldistancescorrespondingtotheminimaof energy, we have varied chiral indices n1 and n2 of the constituent single-wall (SW) nanotubes…

Ab initio hybrid DFT calculations of BaTiO3 bulk and BaO-terminated (001) surface F-centers

Using a supercell model and a hybrid B3PW exchange-correlation functional, we have performed first principles calculations for the F-center in the BaTiO3 bulk and on the BaO-terminated (001) surface. We find that two Ti atoms nearest to the bulk F-center are repulsed, while nearest eight oxygen and four barium atoms relax toward the oxygen vacancy (by 1.06, 0.71 and 0.08% of the lattice constant [Formula: see text], respectively). The magnitudes of atomic displacements around the F-center located on the BaO-terminated (001) surface in most cases (except for Ti) are larger than those around the bulk F-center (0.1, 1.4 and 1.0% of [Formula: see text], respectively). Our calculated BaTiO3 bul…

BacSr1−cTiO3 perovskite solid solutions: Thermodynamics from ab initio electronic structure calculations

We suggest theoretical prediction for Ba"cSr"1"-"cTiO"3 perovskite solid solutions (BST) combining ab initio DFT/B3PW calculations and alloy thermodynamics. This approach is based on calculations of a series of ordered super-structures in Ba-Sr simple cubic sublattice immersed in the rest TiO"3 matrix. Although these structures are unstable with respect to the decomposition, the results of total energy calculations allow us to extract the necessary energy parameters and to calculate the phase diagram for the solid solutions (alloys). A novel approach applied to the BST system enables to predict that at T>400 K Ba and Sr atom distribution is random. But below this temperature at small c Ba a…

Ab initio simulations on Frenkel pairs of radiation defects in corundum

Large scale first principles periodic calculations based on the density functional theory within the localized atomic orbital approach (DFT-LCAO) using the hybrid exchange- correlation potential B3PW have been performed in order to study the structural and electronic properties of radiation-induced Frenkel pairs Oi+VO in corundum crystal. As an initial approach, we have used conventional 2x2x1 supercell for defective α-Al2O3 lattice containing 120 atoms. After relaxation of the ideal supercell structure, the optimized doi-vo distance has been found to be ~4.5 A while the formation energy of Frenkel pair has achieved 11.7 eV. The interstitial Oi atom, both single and a component of Oi+VO pai…

Study of the electronic and atomic structure of thermally treated SrTiO3(110) surfaces

The electronic structure of heated SrTiO3(110) surfaces was investigated with metastable impact electron spectroscopy and ultraviolet photoelectron spectroscopy (He(I). Scanning tunnelling microscopy and atomic force microscopy (AFM) were used to study the topology of the surface. The crystals were heated up to 1000 °C under reducing conditions in ultrahigh vacuum or under oxidizing conditions in synthetic air for 1 h, respectively. Under both conditions microfacetting of the surface is observed. The experimental results are compared with ab initio Hartree-Fock calculations, also presented here, carried out for both ideal and reconstructed SrTiO 3(110) surfaces. The results give direct evid…

Atomic and electronic structure of perfect and defective PbZrO3 perovskite: Hybrid DFT calculations of cubic and orthorhombic phases

Abstract The structural and electronic properties of pure cubic and low-temperature orthorhombic PbZrO3 (antiferroelectric phase), as well as cubic PbZrO3 containing single F-centers (neutral oxygen vacancies) have been simulated by means of ab initio hybrid density functional calculations. We observed a substantial increase of the Pb–O bond covalency in ideal orthorhombic PbZrO3 with respect to its cubic phase. Relatively large displacement of four Pb atoms nearest to the F-center (0.25 A towards the defect) could affect the PbZrO3 ferroelectric properties. An O vacancy in the bulk PbZrO3 attracts ≈0.7 e, and the remaining electron density from the missing O2− is localized mostly on four n…

Fast-Response Single-Nanowire Photodetector Based on ZnO/WS 2 Core/Shell Heterostructures

This work was supported by the Latvian National Research Program IMIS2 and ISSP project for Students and Young Researchers Nr. SJZ/2016/6. S.P. is grateful to the ERA.Net RUS Plus WATERSPLIT project no. 237 for the financial support. S.V. is grateful for partial support by the Estonian Science Foundation grant PUT1689.

Ab initiothermodynamics ofBacSr(1−c)TiO3solid solutions

Based on ab initio calculations for a number of the ${\mathrm{Ba}}_{\mathrm{c}}{\mathrm{Sr}}_{(1\ensuremath{-}\mathrm{c})}\mathrm{Ti}{\mathrm{O}}_{3}$ (BST) superlattices, we developed a thermodynamic approach to these solid solutions. In particular, we calculate the BST phase diagram and show that at relatively low temperatures (below $400\phantom{\rule{0.3em}{0ex}}\mathrm{K}$ for $c=0.5$ and $300\phantom{\rule{0.3em}{0ex}}\mathrm{K}$ for $c=0.1$) the spinodal decomposition of the solid solution occurs. As a result, we predict for small Ba concentrations formation of $\mathrm{Ba}\mathrm{Ti}{\mathrm{O}}_{3}$ nanoregions in a predominantly $\mathrm{Sr}\mathrm{Ti}{\mathrm{O}}_{3}$ matrix and …

Adsorption of atomic and molecular oxygen on the SrTiO3(001) surfaces: Computer simulations by means of hybrid density functional calculations and ab initio thermodynamics

AbstractAb initio calculations based on density functional theory (DFT) have been used to study the energetics, fully relaxed structure, charge redistribution, and electronic density of states of adsorbed atomic and molecular oxygen on defectless unreconstructed SrO- and TiO2-terminated SrTiO3(001) surfaces. Exchange-correlation functional applied within DFT contains a “hybrid” of the non-local Hartree–Fock exchange, DFT exchange, and generalized gradient approximation correlation functionals. The calculations are performed on periodically repeated systems (two-dimensional slabs) large enough for the adsorbed species to be treated as isolated. We find substantial binding energies of up to 1…

Electronic structure and thermodynamic stability ofLaMnO3andLa1−xSrxMnO3(001) surfaces:Ab initiocalculations

We present the results of ab initio hybrid density-functional calculations of the atomic and the electronic structures of ${\text{LaMnO}}_{3}$ (LMO) and ${\text{La}}_{1\ensuremath{-}{x}_{b}}{\text{Sr}}_{{x}_{b}}{\text{MnO}}_{3}$ (001) surfaces. The total energies obtained from these calculations were used to analyze thermodynamic stability of the surfaces. We predict Sr and O vacancy segregation to the surface to occur with similar energies ($\ensuremath{\sim}0.5\text{ }\text{eV}$ per defect). In pure LMO only ${\text{MnO}}_{2}$ termination is thermodynamically favorable under typical operational conditions of a cathode in solid oxide fuel cells, whereas Sr doping makes La(Sr)O termination …

2D Slab Models of Nanotubes Based on Tetragonal TiO2 Structures: Validation over a Diameter Range

This research was funded by the M-ERA.NET project ?Multiscale computer modelling, synthesis and rational design of photo(electro)catalysts for efficient visible-light-driven seawater splitting? (CatWatSplit). Institute of Solid State Physics, University of Latvia as the Center of Excel-lence has received funding from the European Union?s Horizon 2020 Framework Program H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under Grant Agreement No. 739508, project CAMART2.

Growth and characterization of PbI2-decorated ZnO nanowires for photodetection applications

Financial support provided by Scientific Research Project for Students and Young Researchers Nr. SJZ/2017/1 realized at the Institute of Solid State Physics, University of Latvia is greatly acknowledged. The authors are grateful to Liga Bikse for XRD measurements.

Ab initio simulations on the atomic and electronic structure of single-walled BN nanotubes and nanoarches

To simulate the perfect single-walled boron nitride nanotubes and nanoarches with armchair- and zigzag-type chiralities and uniform diameter of � 5 nm, we have constructed their one-dimensional (1D) periodic models. In this study, we have compared the calculated properties of nanotubes with those for both hexagonal and cubic phases of bulk: bond lengths, binding energies per B–N bond, effective atomic charges as well as parameters of total and projected one-electron densities of states. For both phases of BN bulk, we have additionally verified their lattice constants. In the density functional theory (DFT), calculations performed using formalism of the localized Gaussian-type atomic functio…

The impact of temperature on electrical properties of polymer-based nanocomposites

This work was supported by National Research Foundation of Ukraine, project 2020.02/0217. IK would also like to thank VIAA, State Education Development Agency for Latvian state fellowship. HK would like to thank Ministry of Education and Science of Ukraine, project for young researchers No. 0119U100435. In addition, SP and AAP are thankful for financial support from Latvian Council of Science via grant lzp-2018/2-0083. HK and AAP are grateful for the support from the COST Action CA17126.

Ab initiomodeling of sulphur doped TiO2nanotubular photocatalyst for water-splitting hydrogen generation

In order to construct an efficient visible-light-driven TiO2 photocatalyst for water splitting applications, one has to perform improvements of its electronic structure. In this theoretical study we consider single-walled anatase TiO2 nanotubes having following morphologies: (101) 3-layered wall with chirality indexes (n,0) and (n,n), (101) 6-layered wall with (n,0) and (0,n), (001) 6-layered wall with (n,0) and (0,n), and (001) 9-layered wall with (n,0) and (0,n). The latter configuration occurs to be the most energetically stable, due to possessing negative strain energy. In our study the most stable 9-layered anatase (001) (0,n) nanotube has been doped with sulphur. According to obtained…

Ab initio calculations of PbTiO 3 /SrTiO 3 (001) heterostructures

We performed ab initio calculations for the PbTiO3/SrTiO3 (001) heterostructures. For both PbO and TiO2-terminations of the PbTiO3 (001) thin film, augmented on the SrTiO3 (001) substrate, the magnitudes of atomic relaxations Δz increases as a function of the number of augmented monolayers. For both terminations of the augmented PbTiO3 (001) nanothin film, all upper, third and fifth monolayers are displaced inwards (Δz is negative), whereas all second, fourth and sixth monolayers are displaced outwards (Δz is positive). The B3PW calculated PbTiO3/SrTiO3 (001) heterostructure band gaps, independently from the number of augmented layers, are always smaller than the PbTiO3 and SrTiO3 bulk band…

First principles simulations of F centers in cubic SrTiO 3

Atomic and electronic structure of regular and O-deficient SrTiO3 have been studied. Several types of first principles atomistic simulations: Hartree-Fock method, Density Functional Theory, and hybrid HF-DFT functionals, have been applied to periodic models that consider supercells of different sizes (ranging between 40 and 240 atoms). We confirm the ionic character of the Sr-O bonds and the high covalency of the Ti-O2 substructure. For the stoichiometric cubic crystal; the lattice constant and bulk modulus correctly reproduce the experimental data whereas the band gap is only properly obtained by the B3PW functional. The relaxed geometry around the F center shows a large expansion of the t…

Ab initio study of the SrTiO3, BaTiO3 and PbTiO3 (001) surfaces

The results of first-principles calculations of the two possible terminations of (0 0 1) surfaces of SrTiO 3 (STO), BaTiO3 (BTO) and PbTiO3 (PTO) perovskites are presented. Surface atomic structures and their electronic configurations have been calculated using ab initio density functional theory (DFT) combined with hybrid (B3PW) exchange-correlation technique. Our results are compared with previous quantum mechanical calculations and available experimental data. Surface relaxations and the electronic states near valence band gap are discussed in details for all three perovskites. © 2004 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Raman spectra of vacancy-containing LiF: Predictions from first principles

Abstract The electronic structure and Raman scattering from face-centered cubic LiF with three types of vacancies — an F-center, an F ′ -center and a vacancy without electrons ( v F ) — has been calculated by means of hybrid exchange–correlation functional within density functional theory. Our modeling predicts the effective charge of 0.87 e , 1.50 e and 0.10 e on the defect, respectively. The F-center induces two in-gap energy levels for two spin states split by 3.4 eV, while the F ′ -center and the v F induce a single in-gap level 3.8 eV and 2.9 eV below the bottom of conduction band, respectively. The calculated Raman spectra are thoroughly discussed and are found to match well the earli…

Atomic structure of manganese-doped yttrium orthoaluminate

Abstract Using hybrid exchange-correlation functional within density functional theory we have performed first-principle total energy calculations of Mn-doped yttrium orthoaluminate (YAlO3). Its equilibrium atomic structure has been predicted through optimization of coordinates of all atoms using a supercell approach. In our research both Mn3+ and Mn2+ ions have been substituted for the host alumina atom at orthorhombic Pbnm unit cell of YAlO3. F-center has been implemented as charge-compensating defect in case, when Mn2+ dopant is under study. In this study we thoroughly analyze the atomic displacements in seven nearest to Mn ion coordination spheres. Insertion of isoelectronic substitutio…

2D slab models of TiO2 nanotubes for simulation of water adsorption: Validation over a diameter range

Financial support provided by Scientific Research Project for Students and Young Researchers Nr. SJZ/2019/2 realized at the Institute of Solid State Physics, University of Latvia is greatly acknowledged. Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under Grant Agreement No. 739508, project CAMART 2 .

The electronic and atomic structure of SrTiO3, BaTiO3, and PbTiO3(001) surfaces: Ab initio DFT/HF hybrid calculations

In our first-principles study, the electronic properties of the (001) surfaces of three key perovskite crystals, namely SrTiO"3 (STO), BaTiO"3 (BTO), and PbTiO"3 (PTO), have been calculated by means of the density functional theory (DFT) using the exchange-correlation functional containing ''hybrid'' of the non-local Hartree-Fock (HF) exchange, DFT exchange, and Generalized Gradient Approximation (GGA) correlation functionals, commonly known as B3PW. Such a technique allows us to get the optical bulk band gap very close to experiment unlike previous calculations of perovskites. Special attention is paid to careful calculations of the surface rumpling and change of the distances between thre…

Comparative analysis of the electronic structures of mono- and bi-atomic chains of IV, III–V and II–VI group elements calculated using the DFT LCAO and LACW methods

Using the first principle non-relativistic linear combination of atomic orbitals (LCAO) and relativistic linearized augmented cylindrical wave (LACW) methods, the band structure of the covalent and partially ionic ANB8−N single atom width chain is calculated. Both the LCAO and LACW methods show that the chains of C, Si, Ge, Sn, and Pb are metallic. However, there is a great difference between the relativistic and non-relativistic band structures. The π bands crossing the Fermi level are orbitally doubly degenerate in the non-relativistic model. The relativistic LACW calculations demonstrate that the spin and orbital motion of electrons are coupled, thereby splitting the π bands. The spin–or…

Influence of Stress on Electronic and Optical Properties of Rocksalt and Wurtzite MgO–ZnO Nanocomposites with Varying Concentrations of Magnesium and Zinc

The financial support of M-ERA.NET project “ZnMgO materials with tunable band gap for solar-blind UV sensors” (ZMOMUVS) is greatly acknowledged. The Institute of Solid State Physics, University of Latvia, as the Center of Excellence, has received funding from the European Union’s Horizon 2020 Framework Program H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement no. 739508, project CAMART2. The calculations were performed at the Latvian SuperCluster (LASC) located at the Institute of Solid State Physics, University of Latvia.

Systematic Trends in Hybrid-DFT Computations of BaTiO3/SrTiO3, PbTiO3/SrTiO3 and PbZrO3/SrZrO3 (001) Hetero Structures

We acknowledge the financial support from the funder—Latvian Council of Science. The funding number is: Grant No. LZP-2020/1-0345. The Institute of Solid State Physics, University of Latvia (Latvia), as the Centre of Excellence, has received funding from the European Unions Horizon 2020 Framework Programme H2020-WIDESPREAD01-2016-2017-Teaming Phase2 under Grant Agreement No. 739508, project CAMART-2.

Doped 1D Nanostructures of Transition-metal Oxides: First-principles Evaluation of Photocatalytic Suitability