Ab Initio Results Research Articles

Nature of Scapolite Color: Ab Initio Calculations, Spectroscopy, and Structural Study

The article describes the results of a comprehensive study of the extra-framework components of scapolites using quantum–chemical calculations, electronic and vibrational spectroscopy, and single-crystal X-ray diffraction and crystal structure refinement. The ab initio calculations were performed using an embedded-cluster approach of extra-framework components in various cation surroundings. As a result, through comparing the experimental and ab initio calculation results, the energies of the electronic and vibrational transitions of various extra-framework components (CO3)2−, (CO3)·−, S3·−, S2·−—as well as the role of these components in the process of the lowering of the symmetry—were determined for scapolites belonging to the marialite–meionite solid–solution series. The nature of the various colors of the scapolites has also been established. Colors from purple to blue are a result of the presence of radiation-induced pairs of defects: carbonate radical anions (CO3)·− and F-centers. However, polysulfide S3·− radical anions are found in some violet scapolites.

Ab initio calculations of anomalous seniority breaking in the πg9/2 shell for the N = 50 isotones

We performed ab initio valence-space in-medium similarity renormalization group (VS-IMSRG) calculations based on chiral two-nucleon and three-nucleon interactions to investigate the anomalous seniority breaking in the neutron number N=50 isotones: 92Mo, 94Ru, 96Pd, and 98Cd. Our calculations well reproduced the measured low-lying spectra and electromagnetic E2 transitions in these nuclei, supporting partial seniority conservation in the first πg9/2 shell. Recent experiments have revealed that, compared to the symmetric patterns predicted under the conserved seniority symmetry, the 41+→21+E2 transition strength in 94Ru is significantly enhanced and that in 96Pd is suppressed. In contrast, the 61+→41+ and 81+→61+ transitions exhibit the opposite trend. We found that this anomalous asymmetry is sensitive to subtle seniority breaking effects, providing a stringent test for state-of-the-art nucleon-nucleon interactions and nuclear models. We analyzed the anomalous asymmetry using VS-IMSRG calculations across various valence spaces. Our ab initio results suggest that core excitations of both proton and neutron across the Z=50 shell are ascribed to the observed anomalous seniority breaking in the N=50 isotones.

Melting temperature of iron under the Earth’s inner core condition from deep machine learning

Constraining the melting temperature of iron under Earth’s inner core conditions is crucial for understanding core dynamics and planetary evolution. Here, we develop a deep potential (DP) model for iron that explicitly incorporates electronic entropy contributions governing thermodynamics under Earth’s core conditions. Extensive benchmarking demonstrates the DP’s high fidelity across relevant iron phases and extreme pressure and temperature conditions. Through thermodynamic integration and direct solid–liquid coexistence simulations, the DP predicts melting temperatures for iron at the inner core boundary, consistent with previous ab initio results. This resolves the previous discrepancy of iron’s melting temperature at ICB between the DP model and ab initio calculation and suggests the crucial contribution of electronic entropy. Our work provides insights into machine learning melting behavior of iron under core conditions and provides the basis for future development of binary or ternary DP models for iron and other elements in the core.

New theoretical insights on the nonradiative relaxation mechanism of the core structure of mycosporines: The amino-cyclohexenone central template.

We present a comprehensive computational study describing the excited state dynamics and consequent photostability of amino-cyclohexenone (ACyO), the central template of mycosporine systems, widely recognized for their photoprotection of aquatic species. Photoexcitation to the first excited electronic state (S1, 1nπ*) of ACyO is considered an optically dark transition, while photoexcitation to the second excited electronic state (S21ππ*) is an optically bright 1ππ* transition and largely responsible for UV absorption properties of this molecule. We show that following initial photoexcitation to S2, ACyO relaxes via two competing deactivation mechanisms, each mediated by an S1/S0 conical intersection, which directs the excited state population to the electronic ground state (S0). Our abinitio computational results are supported with nonadiabatic dynamics simulation results, yielding an excited state lifetime of ∼280fs for this system in vacuo. These results explain the inherent photostability of this core structure, commonplace in a wide range of microorganisms.

Ab initio study of the interaction between the charged system (FH+) and the He atom

We investigated the molecular structure and spectroscopic properties of the charged system (FH+) in interaction with a helium atom using an ab initio quantum chemistry approach in Jacobi coordinates. Our study focused on the ground state X2Π of (FH+) with various theoretical methods including UCCSD, UCCSD(T) and UCCSD(T)-F12, alongside basis sets like aug-cc-pVnZ (n = T, Q, 5, and 6) and cc-pVQZ-F12. We evaluated how these methods and basis sets affect the minimum energies We assessed the impact of the methods, basis sets, and extrapolation approaches on the minimum energies. Potential energy surfaces (PES) were generated using the correlated UCCSD(T)-F12 method with cc-pVQZ-F12 for hydrogen and fluorine, and cc-pVQZ-F12/optri for helium. These surfaces, considering spin-orbit coupling, are degenerate for linear geometries (θ=0° and θ=180°) of the (FH+)-He complex and correlate with the doubly degenerate X2Π state of (FH+). Our results reveal a strong anisotropic character at short and intermediate distances and a quasi-isotropic character upon dissociation into FH+ and He. We compared the spectroscopic parameters of the (FH+)-He complex with existing theoretical data, finding that the linear arrangement exhibits the highest stability, consistent with previous results for similar complexes. This conclusion is supported by the Milliken atomic charge distribution and a three-dimensional map of the Molecular Electrostatic Potential. Additionally, we used the LEVEL program, to calculate the bound rovibronic levels of the (FH+)-He complex for angular momentum values Ω=1/2 and Ω=3/2. Utilizing our ab initio results and a general interpolation approach based on the Reproducing Kernel Hilbert Space method, we generated contour maps illustrating the analytical potential for the (FH+)-He system. These findings will be employed to study the stabilities, geometries, energetics, and structures of the FH+ charged system within helium clusters.

How do mirror charge radii constrain density dependence of the symmetry energy?

It has recently been suggested that differences in the charge radii of mirror nuclei (ΔRchmirr) are strongly correlated with the neutron-skin thickness (Rskin) of neutron-rich nuclei and with the slope of the symmetry energy (L). To test this assumption, we present ab initio calculations of Rskin in 48Ca and 208Pb, ΔRchmirr in 36Ca−36S, 38Ca−38Ar, 41Sc−41Ca, 48Ni−48Ca, 52Ni−52Cr, and 54Ni−54Fe mirror pairs, and L. Employing the recently developed 34 chiral interaction samples, identified by the history matching approach, we conduct rigorous statistical analysis of correlations among ΔRchmirr, Rskin and L, accounting for quantified uncertainties from low-energy constants of chiral interaction, chiral effective field theory truncation and many-body method approximation. The ab initio results reveal an appreciable ΔRchmirr−L correlation in fp-shell mirror pairs. However, contrary to previous studies, the present calculation finds that the studied sd-shell mirror pairs do not exhibit any ΔRchmirr−L correlation.

Study of Electronic and Optical Properties of Low-Dimensional Nanosystems by First Principles Calculations

The development of new techniques for material manipulation at the nanoscale, as well as advanced numerical tools for material design, has opened up new prospects in the engineering of novel low-dimensional systems with properties specifically designed for applications in different fields, from photonics to energy conversion. Zero-, one-, and two-dimensional nanosystems show unique electronic, optical, and transport properties that can be tuned, for instance, by size reduction, passivation, and doping. In this talk, we discuss ab-initio results obtained in the study of structural, electronic, and optical properties of low-dimensional systems, in particular focusing on silicon, germanium, and silicon/germanium nanostructures. The analysis of mechanisms that can be exploited to tune Auger recombination and carrier multiplication processes, as well as of those that affect the formation of the band offset (Type I and Type II) at the nanoscale, will be discussed. At the end, effects induced by anion ordering on electronic and optical properties of metal oxynitrides will be analyzed.

Efficient determination of Born-effective charges, LO-TO splitting, and Raman tensors of solids with a real-space atom-centered deep learning approach

We introduce a deep neural network (DNN) framework called the Real-space Atomic Decomposition NETwork (radnet), which is capable of making accurate predictions of polarization and of electronic dielectric permittivity tensors in solids and aims to address limitations of previously available machine learning models for Raman predictions in periodic systems. This framework builds on previous, atom-centered approaches while utilizing deep convolutional neural networks. We report excellent accuracies on direct predictions for two prototypical examples: GaAs and BN. We then use automatic differentiation to efficiently calculate the Born-effective charges, longitudinal optical-transverse optical (LO-TO) splitting frequencies, and Raman tensors of these materials. We compute the Raman spectra, and find agreement with ab initio results. Lastly, we explore ways to generalize the predictions of polarization while taking into account periodic boundary conditions and symmetries.

High-temperature boron partitioning and isotope fractionation between basaltic melt and fluid

In the last two decades, boron has gained significance as a geochemical tracer in mantle studies, particularly related to fluid-mediated processes. In our investigation, we explore how boron and its stable isotopes distribute between basaltic melt and hydrous fluid under conditions relevant to magmatic degassing in the shallow crust (1000–1250 °C, 150–250 MPa). We utilized a synthetic MORB-like composition with added boric-acid isotope standard (NIST-SRM951a) and additional trace elements, subjecting it to varying pressure, temperature, and melt-fluid ratios using an internally heated pressure vessel. The B isotope composition in the quenched glasses were determined through femtosecond laser ablation coupled to a multi-collector inductively-coupled-plasma mass spectrometer. Our experiments revealed that, even at the highest temperatures, boron strongly partitions into the fluid phase, accompanied by significant B isotope fractionation. This leads to an enrichment of the heavy B isotope in the fluid, with a constrained Δ11Bmelt-fluid range of -1.7 ± 0.9‰, consistent with ab-initio modeling results. These findings highlight the potential of B isotopes to trace geochemical processes at elevated temperatures with \\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\Delta}^{11}{{B}}_{melt-fluid}=2.913-9.693\\frac{{10}^{6}}{{{T}}^{2}}$$\\end{document}. Our results have implications for predicting the δ11B of degassed, water-bearing basaltic magmas and estimating the B isotope composition of their mantle source.

Second-harmonic generation tensors from high-throughput density-functional perturbation theory

Optical materials play a key role in enabling modern optoelectronic technologies in a wide variety of domains such as the medical or the energy sector. Among them, nonlinear optical crystals are of primary importance to achieve a broader range of electromagnetic waves in the devices. However, numerous and contradicting requirements significantly limit the discovery of new potential candidates, which, in turn, hinders the technological development. In the present work, the static nonlinear susceptibility and dielectric tensor are computed via density-functional perturbation theory for a set of 579 inorganic semiconductors. The computational methodology is discussed and the provided database is described with respect to both its data distribution and its format. Several comparisons with both experimental and ab initio results from literature allow to confirm the reliability of our data. The aim of this work is to provide a relevant dataset to foster the identification of promising nonlinear optical crystals in order to motivate their subsequent experimental investigation.

UNDULATING POTENTIALS OF RYDBERG Σ+-STATES OF ME-RG MOLECULES: NON-EMPIRICAL TREATMENT OF NA-HE EXCIPLEX

The multi-reference con guration interaction method based on single and double excitations (MR-CISD), l-independent core polarization potential (CPP) and diffuse function-saturated cc-pVQZ and aug-cc-pV5Z basis sets for Na and He atoms, respectively, have been used to perform non-relativistic calculations of potential energy curves and permanent dipole moment functions for the ground and excited electronic states of the exciplex Na-He molecule up to the Na(62S) state. The ab initio results obtained in a wide range of internuclear distances R [1.7, 20.0] (Å) have quantitatively claimed the undulating behavior of interatomic potentials, predicted within the framework of the inelastic scattering theory. It has been established that at large R the interatomic potentials and dipole moments of highly excited (3,6,10)2Σ+ states, converging to Na (n = 4, 5, 62S)+He(22S) atomic limits, are modulated by the nodal structure of the radial Rydberg wave function (n > 3) s-electron of Na atom during its scattering on the remote He atom.

Modeling interactions between rubidium atom and magnetometer cell wall molecules

Magnetometer cell wall coat molecules play an important role in preserving the lifetime of pumped alkali metal atoms for use in magnetometers that are capable of measuring very small magnetic fields. The goal of this study is to help rationalize the design of the cell coat molecules. Rubidium-87 is studied in terms of its interaction with three template cell coat molecules: ethane, ethene, and methyltrichlorosilane (MeTS). Ab initio electronic structure methods are applied to investigate the effect that the coat molecules have on the 2S ground state and 2P excited state of 87Rb. We find that, from the ab initio results, the three template molecules have differing effects, with MeTS having the largest effect on the ground state and ethane or ethene having the largest effect on the non-degenerate excited states.

Ideal two-dimensional electronic structure in bulk lead titanate for superior thermoelectrics

An ideal two-dimensional (2D) electronic structure is revealed in n-type tetragonal perovskite PbTiO3 through first-principle calculations. This opens exciting prospects for its applications in thermal-to-electrical energy conversion. The electronic structure is regarded as ideally 2D when it is highly dispersive only along two axes, while along the remaining axis, it is nearly non-dispersive with a bandwidth smaller than 1 meV – insignificant when compared to thermal energy above room temperature (i.e., kBT ≥ 25.9 meV). As a basis for comparison, the electronic structure of the cubic perovskite SrTiO3 is calculated. It is nonideal 2D with the bandwidth along the less dispersive axis larger than the thermal energy. The ideal 2D electronic structure in PbTiO3 leads to a 2D-like density of states, resembling a step function around the conduction minimum while for SrTiO3, the density of states remains 3D-like with a square-root energy dependence. Consequently, n-type PbTiO3 exhibits superior effective band degeneracy within the Fermi window compared to SrTiO3, even though PbTiO3 is nondegenerate at the conduction band minimum, while cubic SrTiO3 is three-fold degenerate. This demonstrates the important role of the ideality in the 2D electronic structure. The ab-initio results demonstrate the potential of PbTiO3 as a promising thermoelectric material.

Structure Factors for Hot Neutron Matter from AbInitio Lattice Simulations with High-Fidelity Chiral Interactions.

We present the first abinitio lattice calculations of spin and density correlations in hot neutron matter using high-fidelity interactions at next-to-next-to-next-to-leading order in chiral effective field theory. These correlations have a large impact on neutrino heating and shock revival in core-collapse supernovae and are encapsulated in functions called structure factors. Unfortunately, calculations of structure factors using high-fidelity chiral interactions were well out of reach using existing computational methods. In this Letter, we solve the problem using a computational approach called the rank-one operator (RO) method. The RO method is a general technique with broad applications to simulations of fermionic many-body systems. It solves the problem of exponential scaling of computational effort when using perturbation theory for higher-body operators and higher-order corrections. Using the RO method, we compute the vector and axial static structure factors for hot neutron matter as a function of temperature and density. The abinitio lattice results are in good agreement with virial expansion calculations at low densities but are more reliable at higher densities. Random phase approximation codes used to estimate neutrino opacity in core-collapse supernovae simulations can now be calibrated with abinitio lattice calculations.

Combined study of phase transitions in the P2-type NaXNi1/3Mn2/3O2 cathode material: experimental, ab-initio and multiphase-field results

The research of new electrode materials such as sodium intercalation compounds is key to meet the challenges of future demands of sustainable energy storage. For these batteries, the intercalation behavior on the micro-scale is governed by a complex interplay of chemical, electrical and mechanical forces strongly influencing the overall cell performance. The multiphase-field method is a suitable tool to study these multi-physics and bridge the scale from ab-initio methods to the cell level. In this work, we follow a combined approach of experiments, density functional theory (DFT) calculations and multiphase-field simulations to predict thermodynamic and kinetic properties for the P2-type NaXNi1/3Mn2/3O2 sodium-ion cathode material. Experimentally, we obtain the thermodynamic potential and diffusion coefficients at various sodium contents using electrochemical techniques and discuss limitations of the experimentally applied methods. DFT is used to identify stable phases by calculating an energy hull curve. Then, the influence of long-range dispersion interactions and the exchange-correlation functional on the voltage curve is investigated by comparison with experimental results. Finally, multiphase-field simulations are performed based on inputs from experiments and DFT. The fitting of phase-specific chemical free energies from DFT calculations and experimental data is discussed. Our results highlight the thermodynamic consistency of all three approaches close to thermodynamic equilibrium. Furthermore, the phase-field method accurately describes the kinetics of the system including multiple phase transitions, by which we unravel the mechanism of the P2-O2 phase transition in a single crystal under the influence of intercalation reaction, bulk diffusion and elastic deformation. The model is able to predict the kinetic capacity loss depending on charging rate in agreement with C-rate experiments.

Thermoelastic Properties and Thermal Evolution of the Martian Core From Ab Initio Calculated Magnetic Fe‐S Liquid

AbstractAccurate thermoelastic properties and thermal conductivity are crucial for understanding the thermal evolution of the Martian core. A fitting method based on ab initio calculated pressure‐volume‐temperature data was proposed for the formulation of the equation of state with high accuracy, by which the pressure and temperature dependent thermoelastic properties can be directly calculated by definitions. Ab initio results showed that Fe0.75S0.25 liquid under Martian core conditions was thoroughly in a magnetic state without existing spin crossover. The Fe0.75S0.25 liquid in magnetic calculations had a low thermal conductivity (21–23 W/m/K) when compared with non‐magnetic calculations at the same state. Based on Insight's estimated Martian core properties (Stähler et al., 2021, https://doi.org/10.1126/science.abi7730) and ab initio calculated properties of the Fe0.75S0.25 liquid, the scenario for the thermal evolution of the Martian core is the iron‐snow model crystallization regime. The parameter uncertainty effect on the cessation time of the dynamo and zone of iron snow was systematically analyzed.

Characterization of iron(III) in aqueous and alkaline environments with abinitio and ReaxFF potentials.

The iron(III) complexes [Fe(H2O)n(OH)m]3-m (n + m = 5, 6, m ≤ 3) and corresponding proton transfer reactions are studied with total energy calculations, the nudged elastic band (NEB) method, and molecular dynamics (MD) simulations using abinitio and a modification of reactive force field potentials, the ReaxFF-AQ potentials, based on the implementation according to Böhm et al. [J. Phys. Chem. C 120, 10849-10856 (2016)]. Applying abinitio potentials, the energies for the reactions [Fe(H2O)n(OH)m]3-m + H2O → [Fe(H2O)n-1(OH)m+1]2-m + H3O+ in a gaseous environment are in good agreement with comparable theoretical results. In an aqueous (aq) or alkaline environment, with the aid of NEB computations, respective minimum energy paths with energy barriers of up to 14.6 kcal/mol and a collective transfer of protons are modeled. Within MD simulations at room temperature, a permanent transfer of protons around the iron(III) ion is observed. The information gained concerning the geometrical and energetic properties of water and the [Fe(H2O)n(OH)m]3-m complexes from the abinitio computations has been used as reference data to optimize parameters for the O-H-Fe interaction within the ReaxFF-AQ approach. For the optimized ReaxFF-AQ parameter set, the statistical properties of the basic water model, such as the radial distribution functions and the proton hopping functions, are evaluated. For the [Fe(H2O)n(OH)m]3-m complexes, it was found that while geometrical and energetic properties are in good agreement with the abinitio data for gaseous environment, the statistical properties as obtained from the MD simulations are only partly in accordance with the abinitio results for the iron(III) complexes in aqueous or alkaline environments.

Exploration of the mechanical properties of carbon-incorporated amorphous silica using a universal neural network potential

C-incorporated amorphous silica (a-SiOC) is expected to be a significant dielectric film for miniaturized semiconductor devices. However, information on the relationship among its composition, atomic structures, and material properties remains insufficient. This study investigated the dependence of the elastic modulus on the C content in a-SiOC, employing a universal neural network interatomic potential to realize a high-accuracy and high-speed simulation of multicomponent systems. The relationship between elastic modulus and atomic network structures was explored by fabricating 480 amorphous structures through the melt-quenching method without predetermined structure assumptions. The bulk modulus increased from 45 to 60 GPa by incorporating 10% C atoms under O-poor conditions and 20% C atoms under O-rich conditions, respectively. This result is attributed to the formation of denser crosslinking atomic network structures. In particular, the C atoms bonded with the Si atoms with higher coordination under O-poor conditions, whereas they tend to bond with O atoms under O-rich conditions, breaking the SiO2 network. Large C clusters precipitated as the C fraction was increased under O-rich conditions. Gas molecules, such as CO and CO2, were also generated. These results are consistent with reported ab initio calculation results of the formation energies of C defects and gas molecules in SiO2. The findings suggest that realizing O-poor conditions during deposition is crucial for fabricating stronger dielectric films. Therefore, this work contributes to understanding the fabrication of stronger dielectric films and elucidating the underlying mechanism of C cluster formation.

Accurate Surface and Finite-Temperature Bulk Properties of Lithium Metal at Large Scales Using Machine Learning Interaction Potentials.

The properties of lithium metal are key parameters in the design of lithium-ion and lithium-metal batteries. They are difficult to probe experimentally due to the high reactivity and low melting point of lithium as well as the microscopic scales at which lithium exists in batteries where it is found to have enhanced strength, with implications for dendrite suppression strategies. Computationally, there is a lack of empirical potentials that are consistently quantitatively accurate across all properties, and ab initio calculations are too costly. In this work, we train a machine learning interaction potential on density functional theory (DFT) data to state-of-the-art accuracy in reproducing experimental and ab initio results across a wide range of simulations at large length and time scales. We accurately predict thermodynamic properties, phonon spectra, temperature dependence of elastic constants, and various surface properties inaccessible using DFT. We establish that there exists a weak Bell-Evans-Polanyi relation correlating the self-adsorption energy and the minimum surface diffusion barrier for high Miller index facets.

Magnetic, transport and topological properties of Co-based shandite thin films

AbstractThe kagome ferromagnet, Co-based shandite Co3Sn2S2, shows a large anomalous Hall effect (AHE) associated with the Weyl nodes. A thin film with a Co kagome monolayer was predicted to exhibit the quantum AHE, which awaits the experimental realisation. However, it is challenging to precisely predict how the Weyl nodes reside in thin films where the lattice and electronic structures are in general different from the bulk. Here we report comprehensive ab initio results for thin films of Co3Sn2S2 with one, two and three Co layers with Sn or S surface terminations. We find that all the Sn-end films stabilise a ferromagnetic state similar to the bulk, and retain the large AHE down to the monolayer limit where the AHE is quantised, while the magnetic and topological properties drastically change with the number of Co layers in the S-end films. Our results would stimulate further experimental exploration of thin Weyl materials.