Ab Initio Density Functional Theory Research Articles

TBMaLT, a flexible toolkit for combining tight-binding and machine learning.

Tight-binding approaches, especially the Density Functional Tight-Binding (DFTB) and the extended tight-binding schemes, allow for efficient quantum mechanical simulations of large systems and long-time scales. They are derived from ab initio density functional theory using pragmatic approximations and some empirical terms, ensuring a fine balance between speed and accuracy. Their accuracy can be improved by tuning the empirical parameters using machine learning techniques, especially when information about the local environment of the atoms is incorporated. As the significant quantum mechanical contributions are still provided by the tight-binding models, and only short-ranged corrections are fitted, the learning procedure is typically shorter and more transferable as it were with predicting the quantum mechanical properties directly with machine learning without an underlying physically motivated model. As a further advantage, derived quantum mechanical quantities can be calculated based on the tight-binding model without the need for additional learning. We have developed the open-source framework-Tight-Binding Machine Learning Toolkit-which allows the easy implementation of such combined approaches. The toolkit currently contains layers for the DFTB method and an interface to the GFN1-xTB Hamiltonian, but due to its modular structure and its well-defined interfaces, additional atom-based schemes can be implemented easily. We are discussing the general structure of the framework, some essential implementation details, and several proof-of-concept applications demonstrating the perspectives of the combined methods and the functionality of the toolkit.

Importance of accurately measuring LDOS maps using scanning tunneling spectroscopy in materials presenting atom-dependent charge order: The case of the correlated Pb/Si(111) single atomic layer

We address here general issues and show how to properly extract the local charge order in two-dimensional systems from scanning tunneling microscopy/spectroscopy (STM/STS) measurements. When the charge order presents spatial variations at the atomic scale inside the unit cell and is energy dependent, particular care should be taken. We show that the widely used lock-in technique performed while acquiring an STM topography in a closed feedback loop cannot be used to extract this local charge order from STS $dI/dV$ differential conductance maps. In such situations, the use of the lock-in technique leads to systematically incorrect $dI/dV$ measurements, giving a false local charge order. We show that a correct method is either to perform a constant height measurement or to perform a full grid of $dI/dV(V)$ spectroscopies, using a set point for the bias voltage outside the bandwidth of the correlated material where the local density of states (LDOS) is expected to be spatially homogeneous. We take as a paradigmatic example of two-dimensional material the 1/3 single-layer Pb/Si(111) phase. As large areas of this phase cannot be grown, charge ordering in this system is not accessible to angular resolved photoemission or grazing x-ray diffraction. Two previous investigations by STM/STS supplemented by ab initio density functional theory (DFT) calculations concluded that this material undergoes a phase transition to a low-temperature $3\ifmmode\times\else\texttimes\fi{}3$ reconstruction where one Pb atom moves up, the two remaining Pb atoms shifting down. A third STM/STS study by Adler et al. [F. Adler, S. Rachel, M. Laubach, J. Maklar, A. Fleszar, J. Sch\"afer, and R. Claessen, Phys. Rev. Lett. 123, 086401 (2019)] came to the opposite conclusion, i.e., that two Pb atoms move up, while one Pb atom shifts down. We show that this latter erroneous conclusion comes from an artifact induced by the lock-in technique. In contrast, using a full grid of $dI/dV$($V$) spectroscopy measurements, our results show that the energy-dependent LDOS maps agree very well with state-of-the-art DFT calculations, confirming the one-up two-down charge ordering. We show that this structural and charge reordering inside the $3\ifmmode\times\else\texttimes\fi{}3$ unit cell is equally driven by electron-electron interactions and the coupling to the substrate.

Ab Initio Simulation of Structure and Properties in Ni-Based Superalloys: Haynes282 and Inconel740.

The electronic structure, interatomic bonding, and mechanical properties of two supercell models of Ni-based superalloys are calculated using ab initio density functional theory methods. The alloys, Haynes282 and Inconel740, are face-centered cubic lattices with 864 atoms and eleven elements. These multi-component alloys have very complex electronic structure, bonding and partial-charge distributions depending on the composition and strength of the local bonding environment. We employ the novel concept of total bond order density (TBOD) and its partial components (PBOD) to ascertain the internal cohesion that controls the intricate balance between the propensity of metallic bonding between Ni, Cr and Co, and the strong bonds with C and Al. We find Inconel740 has slightly stronger mechanical properties than Haynes282. Both Inconel740 and Haynes282 show ductile natures based on Poisson's ratio. Poisson's ratio shows marginal correlation with the TBOD. Comparison with more conventional high entropy alloys with equal components are discussed.

Screening of Alkali Metal-Exchanged Zeolites for Nitrogen/Methane Separation.

Methane (CH4) is the primary component of natural gas and must be purified to a certain level before it can be used as pipeline gas or liquified natural gas (LNG). In particular, nitrogen (N2), a common contaminant in natural gas needs to be rejected to increase the heating value of the gas and meet the LNG product specifications. The development of energy-efficient N2 removal technologies is hampered by N2's inertness and its resemblance to CH4 in terms of kinetic size and polarizability. N2-selective materials are so rare. Here, for the first time, we screened 1425 alkali metal cation exchange zeolites to identify the candidates with the best potential for the separation of N2 from CH4. We discovered a few extraordinary zeolite frameworks capable of achieving equilibrium selectivity toward N2. Particularly, Li+-RRO-3 zeolite with a specific two-dimensional structure demonstrated a selective N2 adsorption capacity of 2.94 mmol/g at 283 K and 1 bar, outperforming the capacity of all known zeolites. Through an ab initio density functional theory study, we found that the five-membered ring of the RRO framework is the most stable cationic site for Li+, and this Li+ can interact with multiple N2 molecules but only one CH4, revealing the mechanism for the high capacity and selectivity of N2. This work suggests promising adsorbents to enable N2 rejection from CH4 in the gas industry without going for energy-intensive cryogenic distillations.

Atomistic investigation of the impact of phosphorus impurities on the tungsten grain boundary decohesion

In the present work, we have generated a new second-nearest neighbour modified embedded atom method potential (2NN-MEAM) for the W–P system to investigate the impact of P impurity segregation on the strength of symmetric 〈110〉 tilt coincident site lattice grain boundaries (GBs) in tungsten. By incorporating the impurity-induced reduction of the work of separation in the fitting strategy, we have produced a potential that predicts decohesion behaviour as found by ab initio density functional theory (DFT) modelling. Analysis of the GB work of separation and generalized stacking fault energy data derived from DFT and the 2NN-MEAM potential show that P-impurities reduce the resistance to both cleavage and slip. Mode I tensile simulations reveal that the most dominant mode of GB failure is cleavage and that pristine GBs, which are initially ductile, on most accounts change to brittle upon introduction of impurities. Such tendencies are in line with experimentally observed correlations between P-impurity content and reduced ductility.

Magnetic properties and coupled spin-phonon behavior in quasi-one-dimensional screw-chain compound BaMn2V2O8

Spin-chain compounds are known to exhibit fascinating magnetic properties, which mostly display magnetic ordering at very low temperatures or remain dynamic even at 0 K. In contrast, the present quasi-one-dimensional spin-chain system $\mathrm{Ba}{\mathrm{Mn}}_{2}{\mathrm{V}}_{2}{\mathrm{O}}_{8}$ exhibits a collinear antiferromagnetic (AFM) long-range ordering at a relatively higher temperature ${T}_{\mathrm{N}}\ensuremath{\sim}37\phantom{\rule{0.16em}{0ex}}\mathrm{K}$, wherein the nearest-neighbor spins have AFM coupling along the spin chain, i.e., along the $c$ axis. The present study also reveals a short-range magnetic ordering prevailing at considerably elevated temperatures above its ${T}_{\mathrm{N}}$. Temperature-dependent Raman spectroscopy demonstrates an occurrence of spin-phonon coupling below ${T}_{\mathrm{N}}$ at least for two phonon modes, whereas the study also shows an unusual thermal evolution of the Raman modes above ${T}_{\mathrm{N}}$, which is apparently associated to the short-range magnetic ordering. Furthermore, extensive ab initio density functional theory calculations accompanied with classical Heisenberg model based theoretical calculations of various exchange interaction parameters $({J}_{0}--{J}_{5})$ suggest an AFM ground state, which matches well with the experimentally obtained spin structure.

Nitrogen rejection in natural gas using NaZSM-25 zeolite.

Natural gas reservoirs usually contain considerable amounts of nitrogen (N2). Methane (CH4) as the main component in natural gas must be purified before transferring to the pipeline or storing as liquified natural gas (LNG). Currently, energy-intensive cryogenic distillation is the only industrial approach for N2 rejection in natural gas. The adsorption process based on a N2-selective adsorbent can minimize the separation cost. However, the search for an adsorbent that can selectively reject N2 in natural gas has lasted for decades. Here, we report a microporous zeolite called NaZSM-25 capable of adsorbing N2 over CH4 with an exceptional selectivity of 47 at room temperature that outperforms all previously known N2-selective adsorbents. At 295 K and 100 kPa, the N2 and CH4 uptakes on NaZSM-25 were 0.25 and 0.005 mmol g-1, respectively. CH4 showed negligible external surface adsorption in the whole temperature range of 273-323 K. Theoretical studies through replica exchanged Monte Carlo, molecular dynamics, and ab initio density functional theory (DFT) proved the diffusion limitation of CH4 as a result of 8-membered ring (8MR) pore opening deformation by Na+ cation. The DFT results showed the diffusion energy barriers of 63 and 96 kJ mol-1 for N2 and CH4, respectively, when passing an 8MR occupied with a Na+. NaZSM-25 is a promising adsorbent to be utilized in a pressure swing adsorption process at room temperature to minimize the energy consumption in N2 rejection units.

Defect pairing in Fe-doped SnS van der Waals crystals: a photoemission and scanning tunneling microscopy study.

We investigate the effect of low concentrations of iron on the physical properties of SnS van der Waals crystals grown from the melt. By means of scanning tunneling microscopy (STM) and photoemission spectroscopy we study Fe-induced defects and observe an electron doping effect in the band structure of the native p-type SnS semiconductor. Atomically resolved and bias dependent STM data of characteristic defects are compared to ab initio density functional theory simulations of vacancy (VS and VSn), Fe substitutional (FeSn), and Fe interstitial (Feint) defects. While native SnS is dominated by acceptor-like VSn vacancies, our results show that Fe preferentially occupies donor-like interstitial Feint sites in close proximity to VSn defects along the high-symmetry c-axis of SnS. The formation of such well-defined coupled (VSn, Feint) defect pairs leads to local compensation of the acceptor-like character of VSn, which is in line with a reduction of p-type carrier concentrations observed in our Hall transport measurements.

The influence of Holmium substitution on the magnetic and mechanical properties of Nd2Fe14B: a first principle study

In this study, the ab initio density functional theory (DFT) approach is used to investigate the effect of Holmium (Ho) on the magnetic and mechanical properties of Nd2Fe14B magnets. Neodymium-based permanent magnets (Nd2Fe14B) are the potential permanent magnets to be used in various applications such as wind turbines and electric vehicles. These magnets possess high magnetic field strength and resistance to demagnetization. However, they suffer from low operating temperatures below 585 K. Substitution of Nd with Ho enhances the magnetic strength of the Nd2Fe14B permanent magnet. NdHoFe14B magnets are found to be thermodynamically stable due to negative heats of formation, which is in good agreement with the calculated density of states. Partial substitution of Nd with Ho improves the stability and the magnetic strength of Nd2Fe14B permanent magnets. The findings will provide insight into the future development of permanent magnetic compounds with good magnetic strength.

Electronic and valleytronic properties of crystalline boron-arsenide tuned by strain and disorder.

Ab initio density functional theory (DFT) and DFT plus coherent potential approximation (DFT + CPA) are employed to reveal, respectively, the effect of in-plane strain and site-diagonal disorder on the electronic structure of cubic boron arsenide (BAs). It is demonstrated that tensile strain and static diagonal disorder both reduce the semiconducting one-particle band gap of BAs, and a V-shaped p-band electronic state emerges - enabling advanced valleytronics based on strained and disordered semiconducting bulk crystals. At biaxial tensile strains close to 15% the valence band lineshape relevant for optoelectronics is shown to coincide with one reported for GaAs at low energies. The role played by static disorder on the As sites is to promote p-type conductivity in the unstrained BAs bulk crystal, consistent with experimental observations. These findings illuminate the intricate and interdependent changes in crystal structure and lattice disorder on the electronic degrees of freedom of semiconductors and semimetals.

A Raman spectroscopic and ab initio investigation of aqueous boron speciation under alkaline hydrothermal conditions: evidence for the structure and thermodynamic stability of the diborate ion.

Raman spectra of aqueous sodium borate solutions, with and without excess NaOH, NaCl, and LiCl, have been obtained from perpendicular and parallel polarization measurements acquired using a custom-built sapphire flow cell over the temperature range 25 to 300 °C at 20 MPa. The solvent-corrected reduced isotropic spectra include a large well-defined band at 865 cm-1 which overlaps with the boric acid B(OH)3 band at 879 cm-1, and becomes increasingly intense at elevated temperatures. This band does not correspond to the spectrum of any other previously reported aqueous polyborate ions, all of which have symmetric stretching bands at frequencies below that of borate, [B(OH)4]-, at 745 cm-1. Based on the classic high-temperature potentiometric titration study by R. E. Mesmer, C. F. Baes and F. H. Sweeton, Acidity measurements at elevated temperatures. VI. Boric acid equilibriums, Inorg. Chem., 1972, 11, 537-543, the new band was postulated to arise from a diborate ion, [B2(OH)7]- or [B2O(OH)5]-. Ab initio density functional theory (DFT), together with chemical modelling studies, suggest that it is most likely [B2(OH)7]-. Thermodynamic formation quotients derived from the peak areas showed variations with ionic strength as well as charge-balance discrepancies, which suggest one or more unidentified minor equilibrium species may also be present. The most likely candidate is the divalent diborate species [B2O2(OH)4]2- which is also predicted to have a band near 865 cm-1 and is postulated to be present as a sodium ion pair. These are the first quantitative Raman spectra ever reported for borate-rich solutions under such conditions and provide the first spectroscopic evidence of a diborate species at PWR reactor coolant temperatures.

Generation of thermal scattering laws with the CINEL code

The thermal scattering laws (TSL) take into account the crystalline structure and atomic motions of isotopes bound in materials. This paper presents the CINEL code, which was developed to generate temperature-dependent TSL for solid, liquid and free gas materials of interest for nuclear reactors. CINEL is able to calculate TSL from the phonon density of states (PDOS) of materials under the Gaussian-Incoherent approximations. The PDOS can be obtained by using theoretical approaches (e.g., ab initio density functional theory and molecular dynamics) or experimental results. In this work, the PDOS presented in the ENDF/BVIII.0 and NJOY-NCrystal libraries were used for numerical validation purposes. The CINEL results are in good agreement with those reported in these databases, even in the specific cases of TSL with the newly mixed elastic format. The coding flexibility offered by Python using the JupyterLab interface allowed to investigate limits of physical models reported in the literature, such as a four-site model for UO2, anharmonic behaviors of oxygen atoms bound in a Fm3m structure, texture in Zry4 samples and jump corrections in a roto-translational diffusion model for liquid water. The use of graphic processing units (GPU) is a necessity to perform calculations in a few minutes. The performances of the CINEL code is illustrated with the results obtained on actinide oxides having a Fm3m structure (UO2, ThO2, NpO2 and PuO2), low enriched fuel (UMo), cladding (Zry4) and moderators (H2O with a specific emphasis on ice).

Machine Learning Diffusion Monte Carlo Forces

Diffusion Monte Carlo (DMC) is one of the most accurate techniques available for calculating the electronic properties of molecules and materials, yet it often remains a challenge to economically compute forces using this technique. As a result, ab initio molecular dynamics simulations and geometry optimizations that employ Diffusion Monte Carlo forces are often out of reach. One potential approach for accelerating the computation of "DMC forces" is to machine learn these forces from DMC energy calculations. In this work, we employ Behler-Parrinello Neural Networks to learn DMC forces from DMC energy calculations for geometry optimization and molecular dynamics simulations of small molecules. We illustrate the unique challenges that stem from learning forces without explicit force data and from noisy energy data by making rigorous comparisons of potential energy surface, dynamics, and optimization predictions among ab initio density functional theory (DFT) simulations and machine-learning models trained on DFT energies with forces, DFT energies without forces, and DMC energies without forces. We show for three small molecules─C2, H2O, and CH3Cl─that machine-learned DMC dynamics can reproduce average bond lengths and angles within a few percent of known experimental results at one hundredth of the typical cost. Our work describes a much-needed means of performing dynamics simulations on high-accuracy, DMC PESs and for generating DMC-quality molecular geometries given current algorithmic constraints.

Acoustic Plasmons in Nickel and Its Modification upon Hydrogen Uptake

In this work, we study, in the framework of the ab initio linear-response time-dependent density functional theory, the low-energy collective electronic excitations with characteristic sound-like dispersion, called acoustic plasmons, in bulk ferromagnetic nickel. Since the respective spatial oscillations in slow and fast charge systems involve states with different spins, excitation of such plasmons in nickel should result in the spatial variations in the spin structure as well. We extend our study to NiHx with different hydrogen concentrations x. We vary the hydrogen concentration and trace variations in the acoustic plasmons properties. Finally, at x=1 the acoustic modes disappear in paramagnetic NiH. The explanation of such evolution is based on the changes in the population of different energy bands with hydrogen content variation.

Advanced materials based on montmorillonite modified with poly(ethylenimine) and poly(2-methyl-2-oxazoline): Experimental and DFT study

This work reports for the first time the ability of inorganic matrix Na-montmorillonite (Mt) to interact with two structurally similar but in term of charge different polymers: linear cationic poly(ethylenimine) (PEI) and non-ionic poly(2-methyl-2-oxazoline) (PMeOx). The effect of various polymer loadings on the interlayer structure and physico-chemical characteristics of composite materials was examined using experimental (XRD, IR, TA analysis) and ab initio Density Functional Theory (DFT) methods. The different charge characteristics of the polymers affected their intercalation into Mt. For PEI-Mt, almost complete exchange of Na+ with PEI cations was found, implying that the PEI chains interacted with the Mt interlayer surface electrostatically. In PMeOx-Mt, the content of Na+ remained the same as in Na-Mt, indicating that PMeOx chains adhered to the Mt surface by hydrogen bonds and/or van der Waals forces. The results showed that PEI could only be intercalated into Mt interlayers up to 100% of the cation exchange capacity (CEC) of Na-Mt; the resulting chains were adsorbed on the Mt outer surface. In contrast, unexpected and very high adsorption of PMeOx on Mt interlayer and outer surfaces, markedly exceeding the CEC of Na-Mt, was discovered for the first time. DFT calculations indicated that both polymers are anchored onto the basal surface of montmorillonite through moderate to weak Cp–Hp∙∙∙ Ob hydrogen bonds. Additional Np–Hp∙∙∙Ob hydrogen bonds in the PEI-Mt structure support the stability of this hybrid structure. Both the PMeOx-Mt and PEI-Mt models showed high stability.

Computational study of adsorption of magnesium polysulfides on VS4 magnesium sulfur batteries

New high-performance battery designs need to be developed to feed the growing needs of electrostatic energy storage. Magnesium-Sulfur (Mg-S) batteries are fast emerging as a promising candidate in the last few years. However, they are plagued by viability issues due to the ‘Shuttle Effect’ slowing down the reaction kinetic and causing rapid decay of battery capacity. The shuttle effect is due to the formation of meta-stable magnesium polysulfides (MgSx) that are soluble in the battery electrolyte. The formation of these polysulfides reduces the efficiency of the cell reaction and causes a loss of electrode material since the polysulfides cannot be recycled. To combat these issues, vanadium tetra sulfide (VS4) has been identified as a potential adsorbent for the MgSx, which can help recycle them and act as a catalyst. In this project, the adsorption capacity of the [110] surface of VS4 towards various MgSx has been computationally investigated by performing ab initio Density Functional Theory (DFT) calculations. The adsorption energies of various MgSx upon adsorption on (VS4) have been calculated. The results are promising, and hint at the good efficacy of (VS4) in Mg-S batteries, similar to Lithium-Sulfur (Li-S) batteries.

Development of a ReaxFF potential for Au–Pd

The bimetallic alloys often outperform their single-component counterparts due to synergistic effects. Being widely known, the Au–Pd alloy is a promising candidate for the novel heterogeneous nanocatalysts. Rational design of such systems requires theoretical simulations under ambient conditions. Ab initio quantum-mechanical calculations employ the density functional theory (DFT) and are limited to the systems with few tens of atoms and short timescales. The alternative solution implies development of reliable atomistic potentials. Among different approaches ReaxFF combines chemical accuracy and low computational costs. However, the development of a new potential is a problem without unique solution and thus requires accurate validation criteria. In this work we construct ReaxFF potential for the Au–Pd system based on ab initio DFT calculations for bulk structures, slabs and nanoparticles with different stoichiometry. The validation was performed with molecular dynamics and Monte-Carlo calculations. We present several optimal parametrizations that describe experimental bulk mechanical and thermal properties, atomic order-disorder phase transition temperatures and the resulting ordered crystal structures.

Sliding induced multiple polarization states in two-dimensional ferroelectrics

When the atomic layers in a non-centrosymmetric van der Waals structure slide against each other, the interfacial charge transfer results in a reversal of the structure’s spontaneous polarization. This phenomenon is known as sliding ferroelectricity and it is markedly different from conventional ferroelectric switching mechanisms relying on ion displacement. Here, we present layer dependence as a new dimension to control sliding ferroelectricity. By fabricating 3 R MoS2 of various thicknesses into dual-gate field-effect transistors, we obtain anomalous intermediate polarization states in multilayer (more than bilayer) 3 R MoS2. Using results from ab initio density functional theory calculations, we propose a generalized model to describe the ferroelectric switching process in multilayer 3 R MoS2 and to explain the formation of these intermediate polarization states. This work reveals the critical roles layer number and interlayer dipole coupling play in sliding ferroelectricity and presents a new strategy for the design of novel sliding ferroelectric devices.

Pressure-induced phase transition and band-gap decrease in semiconducting Na3Bi(IO3)6

We report a combined experimental/theoretical high-pressure study of Na3Bi(IO3)6 under compression to 11.2 GPa at ambient temperature. Through a combination of single-crystal and powder synchrotron X-ray diffraction, optical absorption measurements and ab initio density functional theory calculations we unambiguously show a first-order pressure-induced phase transition at around 9.5 GPa from the ambient pressure phase, referred to here as α-Na3Bi(IO3)6, to a new crystalline structure referred to here as β-Na3Bi(IO3)6. The triclinic (P-1) to triclinic (P1) phase transition is characterised by a doubling of the primitive cell volume, whereby the crystallographic b-axis doubles in length, and by a decrease in the volume per formula unit of approximately 3 %. The phase transition is also characterised by an indirect → indirect electronic bandgap decrease of approximately 0.1 eV as measured by absorption spectroscopy (3.44(1) → 3.32(1) eV) and calculated via density functional calculations (2.48 → 2.33 eV). We also report the pressure evolution of the crystal lattice parameters and isothermal compressibility tensor of the ambient pressure phase α-Na3Bi(IO3)6, which reveals highly anisotropic compressibility and a bulk modulus of 30.4(7) GPa.

Moisture Dependent Degradation Rate of Silicone in LED Optical Housing Material—Ab-Initio Modelling

Degradation of LED housings which make up of polydimethylsiloxanes (PDMS) in outdoor applications has been one of the rising concerns as they reduce the overall lifetime of the LED leading to cost and safety issues. The primary stressors for such LED degradation were found to be humidity and light emitted from the LED dice. The degradation mechanisms are hydrolysis and condensation of PDMS which themselves are interdependent. The degradation rate was also found to be dependent on the humidity level. This work identifies these dependencies, using ab-initio density functional theory and molecular dynamics simulation, and the results agree with the reported experimental data. From the detail understanding of the degradation mechanisms and the identification of the rate determining factors which are moisture level and the level of light absorption in PDMS, acceleration models commonly used for extrapolation are questioned, and new quality indexes of the PDMS are also identified to ensure the durability of LEDs in outdoor applications. Testing method to evaluate these new quality indexes is also proposed.