Electronic Structure Calculations Research Articles

Ab Initio Multiple Spawning Nonadiabatic Dynamics with Different CASPT2 Flavors: A Fully Open-Source PySpawn/OpenMolcas Interface.

We introduce an interface between PySpawn, a simulation package to run ab initio multiple spawning (AIMS) nonadiabatic dynamics, and OpenMolcas, a software package to perform multiconfigurational perturbations theory (CASPT2) electronic structure calculations. Our interface allows us to exploit all the functionalities of the two codes: the modular and efficient Python implementation of the AIMS algorithm and the extensive analysis tools offered by PySpawn, with the cutting-edge implementation of CASPT2 equations in OpenMolcas, including the recently introduced analytical gradients and different flavors. Both are fully open-source and free of charge, making the following implementation unique in the current plethora of software for nonadiabatic dynamics. This represents an important step toward a wider application of AIMS-based nonadiabatic dynamics combined with high-accuracy excited-state calculations. The importance and the need for such an implementation are demonstrated by application to the ultrafast relaxation of fulvene from S1 to S0, which is drastically affected by the potential energy surface on which the nuclear wavepacket is propagated. Additionally, the decay is influenced by the CASPT2 flavor adopted, posing interesting questions in the choice of one over the other and opening the door to deeper studies on the effect of CASPT2 formulations in nonadiabatic dynamics.

Photoionization of aziridine: Nonadiabatic dynamics of the first six low-lying electronic states of the aziridine radical cation.

In this article, the theoretical photoionization spectroscopy of the aziridine (C2H5N) molecule is investigated. To start with, we have optimized the geometry of this molecule at the neutral electronic ground state at the density functional theory/augmented correlation-consistent polarized valence triple zeta level of theory using the G09 program. The electronic structure calculations were restricted to the first six low-lying electronic states in order to account for the experimental photoelectron spectrum of the C2H5N molecule. The first six low-lying electronic states (X̃2A', Ã2A', B̃2A″, C̃2A″, D̃2A', and Ẽ2A') of the potential energy surfaces (PESs) are calculated by both equation of motion-ionization potential-coupled cluster singles and doubles and multi-configuration quasi-degenerate perturbation theory abinitio quantum chemistry methods along the dimensionless normal displacement coordinates in which multiple conical intersections were established among the considered electronic states. A (6 × 6) model vibronic Hamiltonian is constructed on a diabatic electronic basis, using the symmetry selection rules and Taylor series expansion. The Cs symmetry point group of the aziridine molecule leads to electronic states symmetry of either A' or A″, and these states are close in energy, due to which the same symmetry electronic states avoid each other. To get a smooth diabatic PES, a fourfold diabatization scheme is used, which is implemented in the General Atomic and Molecular Electronic Structure Systems suite of programs. All the parameters used in the diabatic vibronic coupling model Hamiltonian are calculated in terms of the normal modes of vibrational coordinates. Finally, the vibronic model Hamiltonian constructed for the coupled six electronic states is used to solve both time-independent and time-dependent Schrödinger equations using the multi-configuration time-dependent Hartree program module to obtain the dynamical observables. The theoretical vibronic band structure is found to be in good accord with the available experimental results.

Investigating the structural, electronic, and optical properties of the novel double perovskite K2AgBiI6 using DFT

In this groundbreaking study, we unveil the remarkable structural, electronic, and optical Properties of the newly discovered double perovskite material, K2AgBiI6, presenting a paradigm shift in materials science. The unique crystal structure and diverse atomic interactions inherent in this double perovskite make it an up-and-coming candidate for various technological applications, particularly in photovoltaics; owing to its stability and resistance to heat and humidity, we aim to shed light on the extraordinary potential of K2AgBiI6. Our study provides valuable insights for researchers engaged in tailored material design. We anticipate that the exceptional electronic properties of K2AgBiI6 will not only redefine the boundaries of materials engineering but also catalyze unprecedented advances in sustainable technology. Employing the powerful computational tool CASTEP, we conducted detailed electronic structure calculations within the framework of Density Functional Theory (DFT) to unravel the electronic properties of the double perovskite K2AgBiI6. Our investigation thoroughly explored structural properties, band structure, total density of states (DOS), and partial density of states (PDOS). Furthermore, we systematically examined the influence of different exchange-correlation functionals, including LDA, GGA, and m-GGA, on the electronic and optical features of the material by presenting a comparative analysis of these approximations.

Accelerating Relativistic Exact-Two-Component Density Functional Theory Calculations with Graphical Processing Units.

Numerical integration of the exchange-correlation potential is an inherently parallel problem that can be significantly accelerated by graphical processing units (GPUs). In this Letter, we present the first implementation of GPU-accelerated exchange-correlation potential in the GauXC library for relativistic, 2-component density functional theory. By benchmarking against copper, silver, and gold coinage metal clusters, we demonstrate the speed and efficiency of our implementation, achieving significant speedup compared to CPU-based calculations. One GPU card provides computational power equivalent to roughly 400 CPU cores in the context of this work. The speedup further increases for larger systems, highlighting the potential of our approach for future, more computationally demanding simulations. Our implementation supports arbitrary angular momentum basis functions, enabling the simulation of systems with heavy elements and providing substantial speedup to relativistic electronic structure calculations. This advancement paves the way for more efficient and extensive computational studies in the field of density functional theory.

Synergy of Experiment and Broadened Exploration of Ab Initio Calculations for Understanding of Lanthanide-Pentacyanidocobaltate Molecular Nanomagnets and Their Optical Properties.

We present a synergistic experimental-theoretical methodology for the investigation of lanthanide-based single-molecule magnets (SMMs), demonstrated using the example of novel heterometallic molecules incorporating Nd3+/Ce3+ ions combined with three different, rarely explored, pentacyanidocobaltate(III) metalloligands, [CoIII(CN)5(azido/nitrito-N/iodido)]3-. The theoretical part of our approach broadens the exploration of ab initio calculations for lanthanide(III) complexes toward the convenient simulations of such physical characteristics as directional dependences of Helmholtz energy, magnetization, susceptibility, and their thermal and field evolution, as well as light absorption and emission bands. This work was conducted using newly designed SlothPy software (https://slothpy.org). It is introduced as an open-source Python library for simulating various physical properties from first-principles based on results of electronic structure calculations obtained within popular quantum chemistry packages. The computational results were confronted with spectroscopic and ac/dc-magnetic data, the latter analyzed using previously designed relACs software. The combination of experimental and computational methods gave insight into phonon-assisted magnetic relaxation mechanisms, disentangling them from the temperature-independent quantum tunneling of magnetization and emphasizing the role of local-mode processes. This study provides an understanding of the changes in lanthanide(III) magnetic anisotropy introduced with pentacyanidocobaltates(III) modifications, theoretically exploring also potential applications of reported compounds as anisotropy switches or optical thermometers.

Microsolvation of a Proton by Ar Atoms: Structures and Energetics of ArnH Clusters+

We present a computational investigation on the structural arrangements and energetic stabilities of small-size protonated argon clusters, ArnH+. Using high-level ab initio electronic structure computations, we determined that the linear symmetric triatomic ArH+Ar ion serves as the molecular core for all larger clusters studied. Through harmonic normal-mode analysis for clusters containing up to seven argon atoms, we observed that the proton-shared vibration shifts to lower frequencies, consistent with measurements in gas-phase IRPD and solid Ar-matrix isolation experiments. We explored the sum-of-potentials approach by employing kernel-based machine-learning potential models trained on CCSD(T)-F12 data. These models included expansions of up to two-body, three-body, and four-body terms to represent the underlying interactions as the number of Ar atoms increases. Our results indicate that the four-body contributions are crucial for accurately describing the potential surfaces in clusters with n> 3. Using these potential models and an evolutionary programming method, we analyzed the structural stability of clusters with up to 24 Ar atoms. The most energetically favored ArnH+ structures were identified for magic size clusters at n = 7, 13, and 19, corresponding to the formation of Ar-pentagon rings perpendicular to the ArH+Ar core ion axis. The sequential formation of such regular shell structures is compared to ion yield data from high-resolution mass spectrometry measurements. Our results demonstrate the effectiveness of the developed sum-of-potentials model in describing trends in the nature of bonding during the single proton microsolvation by Ar atoms, encouraging further quantum nuclear studies.

Crystal structure re-determination of binary IrAl2.75 into Ir8Al21.22

The Ir8Al21.22 binary intermetallic compound was synthesized using arc melting technique. Its crystal structure probed by single-crystal X-ray diffraction is a superstructure variant of the previously reported cubic IrAl2.75 compound. Ir8Al21.22 crystallizes in the Fmm2 space group with the unit cell parameters of a = 15.3307(9) Å, b = 15.3226(10) Å, c = 15.3129(9) Å, and V = 3597.1(4) Å3. The crystal structure contains columns of interpenetrating distorted icosahedral clusters – a characteristic feature of the approximant phases and quasicrystals. Electronic structure calculations indicate strong hybridization between valence orbitals of iridium and aluminum atoms accompanied by the formation of pseudogap, which separates the valence and conduction bands.

Optical response of Zr[formula omitted]CO[formula omitted]/MoS[formula omitted] van der Waals heterostructures calculated using first-principles calculations

In the field of material science, the search for a material with an optimal bandgap of approximately 1.40 eV that can act as an efficient photocatalyst for water splitting using solar spectrum irradiation is a noble mission. In this article, we explore the structural, electronic structure, optical and photocatalytic properties of Zr2CO2/MoS2 vdW heterostructures. Our results demonstrates that the Zr2CO2/MoS2 vdW heterostructure can be reliably synthesized. This is due to a minimal lattice mismatch of less than 3%, a negative adhesion energy of -4.23 meV/Å 2, and inherent dynamic stability. The electronic band structure calculations indicate that the Zr2CO2/MoS2 vdW heterostructure is an indirect bandgap semiconductor. We found that the conduction band minimum (CBM) and valance band maximum (VBM) of the heterostructure are located in different monolayers. Furthermore, under −2% biaxial strain a transition from type-I to type-II (staggered) band alignment occurred. Stacking 2D MoS2 on the Zr2CO2 monolayer results in a vdW heterostructure, and as a result, the HSE calculated bandgap of the Zr2CO2/MoS2 vdW heterostructure in most stable configuration lying in the ideal range for photocatalytic applications. We also studied the heterostructure’s optical properties to understand its response to incident photons with energies up to 14 eV. Based on our findings, Zr2CO2/MoS2 heterostructures are desirable for optoelectronic device applications operated in visible range. Our research offers fresh recommendations for developing novel, highly effective photocatalytic compounds with numerous optical device applications.

Ni thin-films on Pd surfaces and effects of oxygen adsorption: Ab-initio study of structures, electronic properties, magnetic anisotropy

We report first-principles electronic structure calculations of the structural, electronic, and magnetic properties of model epitaxial layers consisting of nickel (Ni) atomic layers deposited on palladium (Pd) substrate, i.e., Ni(001)m∣Pd(001)n where m=1,2,6 and n=3,10, are layer thicknesses. We also investigate the effect of oxygen adsorption on the calculated properties. We found variation in magnetization of between ≈0.6μB to 1.00 μB across the nickel layers. Also, finite magnetic moments albeit of small values of between 0.2 μB and 0.3 μB is found on the Pd at the interface. This magnetic moment on an otherwise non-magnetic Pd atoms has been adduced to interfacial strain due to lattice mismatch between the Ni and Pd layers at the Ni|Pd interface. The effect of adsorbed oxygen on the Nim∣Pdn is that it increases the magnetic moment on the nickel layers. Also, regarding the magnitude of magnetic anisotropy energy (MAE), we found a high perpendicular values of 1.63 meV and 1.37 meV per unit cell respectively for Nim∣Pd10 (m=2,6) which are relatively higher than those reported for other transition metal epitaxial layers. However, the presence of oxygen atom on the Ni∣Pd changes the direction and magnitude of MAE. Indeed, O adsorption favours or enhances in-plane magnetization direction depending on the thickness of the Ni layers for a fixed Pd thickness. Plots of local density of states (LDOS) which include the effect of spin–orbit coupling (SOC), show that in the case of Ni∣Pd having perpendicular MAE, there appears a new SOC-induced electronic states below and above the Fermi level. These states appears to stabilize this type of magnetic anisotropy. On the other hand, in-plane MAE is characterized by SOC-induced localized states below the Fermi level (EF) as well as the lowering of the DOS at the EF. Our work explores the physical, magnetic and electronic properties that may be useful in designing Ni∣Pd-based superlattices for magnetic or spintronic applications.

Synthesis, structure, supramolecular assembly inspection by Hirshfeld surface analysis, DFT study and molecular docking inspection of 4,5-bis(2-chlorophenyl)-8a-phenylhexahydropyrimido[4,5-d]pyrimidine-2,7(1H,3H)-dithione

We studied the three-component condensation of 2-chloraldehyde, acetophenone, and thiourea in conjunction with HCl, resulting in the formation of a new compound: 4,5-bis(2-chlorophenyl)-8a-phenylhexahydropyrimido[4,5-d]pyrimidine-2,7(1H,3H)-dithione (CPPD). The compound's structure was affirmed via X-ray diffraction study. The asymmetric unit contained two molecules that were independent relative to crystallography and an ethanol solvent. The difference between independent molecules was explored by dihedral angles between similar rings in both molecular. The difference between molecules was further explored by molecular overlay plot. The supramolecular assembly was supported via diverse intermolecular interactions which were studied through the use of Hirshfeld surface analysis. Electronic structure computations were carried out at the ωb97xd/tzvp level. Natural bonding orbital (NBO), and FMO study reveal reactivity and charge transfer mechanisms within the compound. Furthermore, the nature of bonding in the present molecule is characterized through quantum theory of atoms in molecules (QTAIM), ELF, and LOL studies. Ab-initio molecular dynamic (AIMD) revealed the kinetic and thermodynamic stability at 300 K. The DFT results have excellent correlation with experimental data. The molecular docking and molecular dynamics simulation further revealed the compound to get deep access in the active pocket of type 2 anti-diabetes GLUT4 protein. This was validated by the stable dynamics as demonstrated by the uniform behavior of the root mean square deviation (RMSD) plot. The root mean square fluctuation (RMSF) also showed stable interactions with amino acids in the presence of the compound. Further, simulation trajectories on the basis of binding free energies indicate the significant role of van der Waals force in the formation of the intermolecular docked complex. This concluded the compound might be a potent structure for the development of anti-diabetic compounds.

Design of Charge Transfer Donor-Acceptor Co-Crystals with Long Lived Charge Carriers

Organic donor-acceptor co-crystals with long exciton lifetimes have emerged as a promising class of semiconductors for their unique photophysical properties. These are crystalline, single-phase materials composed of two or more different compounds in a stoichiometric ratio, providing a platform for unveiling the structure–property relationships at a molecular level. Importantly, co-crystals that are packed through π stacking interactions have the ability to form charge transfer (CT) excitons within donor-acceptor pairs.1,2,3 We hypothesize that co-crystals with a high degree of CT will have longer exciton lifetimes. Therefore, we design and synthesized of new co-crystals using derivatives of N,N-bis(3-pentyl)-perylene-3,4:9,10-bis(dicarboximide) (PDI, acceptor) with a series of donor molecules, including peri-xanthenoxanthene (PXX), perylene, and triphenylene. High quality single crystals were isolated by slow evaporation at room temperature from suitable solvent mixtures. Their crystal structures were successfully refined by single-crystal X-ray diffraction and the phase purity was validated by powder diffraction. Crystal structures revealed that the driving force for forming these co-crystals is π...π stacking. We measured diffuse reflectance UV/visible spectra of each of these co-crystals and compared with computed spectra to assign the observed electronic transitions. DFT calculations provide additional insights into the nature of the excited state CT interactions which can be derived from ground state electronic structure calculations. Transient absorption measurements were conducted to understand their long exciton lifetime for each of as synthesized co-crystals. We conclude that this study supported our previous hypothesis and such materials are potentially useful in applications ranging from photovoltaics and opto-electronics to photocatalysis. References 1) A. Abou Taka, J. E. Reynolds Iii, N. C. Cole-Filipiak, M. Shivanna, C. J. Yu, P. L. Feng, et al. Phys. Chem. Chem. Phys. 2023, 25, 27065.2) L. Sun, Y. Wang, F. Yang, X. Zhang and W. Hu. Adv. Mater. 2019, 31, 1902328.3) I. Schlesinger, N. E. Powers-Riggs, J. L. Logsdon, Y. Qi, S. A. Miller, R. Tempelaar, et al. Chem. Sci., 2020, 11, 9532–9541.

Machine Learning Accelerated Identification of Bifunctional Active Sites in Metal-Organic Framework Derived Metal Oxide Heterostructures for High-Performance Zinc-Air Batteries

The demand for electrochemical energy storage (ESS) systems and their market size has drastically increased in many applications ranging from portable devices through electric vehicles to large-scale grid systems over the past decades. Yet, a more advanced ESS is required due to the safety issues and limited energy density of currently commercialized lithium-ion batteries (LIBs) for wide and matured applications. As a solution to this challenge, zinc-air batteries (ZABs) have gained tremendous attention due to their high energy density, low cost, environmental friendliness, and much lower fire risk characteristics. ZABs utilize oxygen from the atmosphere at their cathode during discharge, where the atmospheric oxygen is reduced to hydroxide via an oxygen reduction reaction (ORR). On the other hand, hydroxide is released as oxygen via oxygen evolution reaction (OER) during charge. The fact that oxygen is drawn directly from the air enables high gravimetric and volumetric energy densities of ZABs compared to those of commercial LIBs. However, the sluggish kinetics of the four-electron transfer steps in ORR and the mass transport of oxygen in OER remain major challenges for the practical application of ZABs. Meanwhile, precious metal-based catalysts such as Pt/C and RuO2 are known to have good catalytic activity towards ORR and OER. However, the integration of different catalysts into the same cathode is very difficult. Additionally, the high cost and natural scarcity of novel metals limit their usage for practical applications.We synthesized a bifunctional CoO/Mn3O4 heterostructure (CMH) OER/ORR electrocatalyst which was derived from metal-organic framework (MOF) for excellent activities in ZABs. The CMH cathode exhibited high ORR and OER performances, as demonstrated by the higher ORR current density than that of the Pt/C catalyst as well as the low OER overpotential exceeding those of the RuO2 catalyst. Remarkably, atomic structures of the CMH were elucidated using global optimization of genetic algorithm integrated with the machine learning force field. By adopting first-principles electronic structure calculations, we further revealed the charge transfer and active sites for both reactions in the identified heterojunction. Furthermore, assembling CMH cathode and Zn metal anode into a ZAB full-cell configuration achieves a ~5.5-fold higher energy density of 879 Wh kg-1 exceeding those of commercial lithium-ion batteries (LIBs), a high-discharge outstanding power density that is 1.39 times higher than novel metal catalysts, and robust cycle stability with negligible voltage decay which is far superior to that of benchmark Pt/C+RuO2 electrocatalysts.

Targeting spectroscopic accuracy for dispersion bound systems from abinitio techniques: Translational eigenstates of Ne@C70.

We investigate the endofullerene system Ne@C70 by constructing a three-dimensional Potential Energy Surface (PES) describing the translational motion of the Ne atom. This is constructed from electronic structure calculations from a plethora of methods, including MP2, SCS-MP2, SOS-MP2, RPA@PBE, and C(HF)-RPA, which were previously used for He@C60 in Panchagnula et al. [J. Chem. Phys. 160, 104303 (2024)], alongside B86bPBE-25X-XDM and B86bPBE-50X-XDM. The reduction in symmetry moving from C60 to C70 introduces a double well potential along the anisotropic direction, which forms a test of the sensitivity and effectiveness of the electronic structure methods. The nuclear Hamiltonian is diagonalized using a symmetrized double minimum basis set outlined in Panchagnula and Thom [J. Chem. Phys. 159, 164308 (2023)], with translational energies having error bars ±1 and ±2 cm-1. We find no consistency between electronic structure methods as they find a range of barrier heights and minima positions of the double well and different translational eigenspectra, which also differ from the Lennard-Jones (LJ) PES given in Mandziuk and Bačić [J. Chem. Phys. 101, 2126-2140 (1994)]. We find that generating effective LJ parameters for each electronic structure method cannot reproduce the full PES nor recreate the eigenstates, and this suggests that the LJ form of the PES, while simple, may not be best suited to describe these systems. Even though MP2 and RPA@PBE performed best for He@C60, due to the lack of concordance between all electronic structure methods, we require more experimental data in order to properly validate the choice.

Rational Design, Synthesis, and Computational Investigation of Dihydropyridine [2,3-d] Pyrimidines as Polyphenol Oxidase Inhibitors with Improved Potency.

Polyphenol oxidase (PPO) is an industrially important enzyme associated with browning reactions. In the present study, a set of ten new dihydropyridine [2,3-d] pyrimidines (TD-Hid-1-10) were synthesized and was found to be proven characteristically by 1H NMR, 13C NMR, IR, elemental analysis, and assessed as possible PPO inhibitors. PPO was purified from banana using three-phase partitioning, achieving an 18.65-fold purification and 136.47% activity recovery. Enzyme kinetics revealed that the compounds TD-Hid-6 and TD-Hid-7 are to be the most potent inhibitors, exhibiting mixed-type inhibition profile with IC50 values of 1.14 µM, 5.29 µM respectively against purified PPO enzyme. Electronic structure calculations at the B3LYP/PBE0 level of theories using def-2 SVP, def2-TZVP basis sets with various molecular descriptors characterized the electronic behavior of studied derivatives TD-Hid-1-10. Molecular electrostatic potential (MEP) and reduced density gradient analyses of RDG-NCI provided insights into charge distributions and weak intermolecular interactions. Docking study simulations predicted binding poses within crucial amino acid sequence in the 2y9x enzyme's active site, which is typically similar in sequence to the PPO form is not allowed. Ligands were analysed in terms of binding energies, inhibitor concentrations (mM) and various molecular interactions such as H-bonds, H-carbon, π-carbon, π-sigma, π-sigma, π-π T-shaped, π-π stacked, π-alkyl, Van der Waals and Cu interactions. The lowest binding energy (-7.83kcal/mol) and the highest inhibitory effect (1.83 mM) were shown by the ligand Td-Hid-6, which forms H-bonds with Met280 and Asn260, exhibits π-sigma interactions with His61 and π-alkyl interactions with Val283. Other ligands also showed different interactions with various amino acids; for example, the Td-Hid-1 ligand formed H-bonds with His244 and showed π-sigma interactions with His244 and Val283.

Emergence of polar skyrmions in 2D Janus CrInX3 (X=Se, Te) magnets

In the realm of multiferroicity in 2D magnets, whether magnetic and polar skyrmions can coexist within a single topological entity has emerged as an important question. Here, we study Janus 2D magnets CrInX3 (X=Se, Te) for a comprehensive investigation of the magnetic ground state, magnetic excited state, and corresponding ferroelectric polarization by first-principles electronic structure calculations and Monte Carlo simulations. Specifically, we have thoroughly elucidated the magnetic exchange mechanisms, and have fully exemplified the magnetic field dependence of the magnon spectrum. More importantly, our study reveals a previously unrecognized, remarkably large spin-spiral-induced ferroelectric polarization (up to 194.9 μC/m2) in both compounds. We propose an approach to identify polar skyrmions within magnetic skyrmions, based on the observed direct correlation between spin texture and polarization density. Elucidating this correlation not only deepens our understanding of magnetic skyrmions but also paves the way for innovative research in the realm of multiferroic skyrmions.

Molecular spectroscopy, solvent effect, and DFT studies of azithromycin solvate

Azithromycin ethanol solvate monohydrate [C38H72N2O120.5(C2H6O)H2O], abbreviated by AZM-MH-EtOH, was synthesized by slow evaporation method and investigated by powder X-ray diffraction, Raman and infrared (IR) spectroscopy combined with density functional theory (DFT) studies. Electronic and vibrational properties were properly investigated based on a theoretical study of solvation effects, using implicit solvation and solute electron density models. The electronic and vibrational studies were evaluated under aqueous, ethanolic, and vacuum conditions. The electronic structure calculations indicated that the AZM-MH-EtOH is chemically more stable in solvents compared to vacuum condition. Ultraviolet–visible (UV–vis) measurements confirmed the stability of the material in ethanolic medium, due to higher absorbance values compared to the aqueous medium. Vibrational changes were observed in the Raman and IR bands, which have connection with hydrogen bonds. The experimental vibration modes showed better accordance with the predicted modes’ values under solvation effects, but a slight divergence is noticed when we compared to vibration modes obtained in vacuum. Furthermore, the results have revealed a greater affinity profile of AZM-MH-EtOH for water and ethanol solvents compared to theoretical data under vacuum condition.

Two-phase/two-gap scenario in heavily reduced superconducting ITO films revealed by point-contact spectroscopy

We present the first point-contact measurements of heavily reduced indium tin oxide (ITO) films in the superconducting state, which simultaneously demonstrate high transparency in the visible light spectrum. Analysis of the differential conductance spectrum indicates the presence of two superconducting phases, the main one with a critical temperature Tc of about 4.6 K and an additional phase with Tc ∼ 10 K, most likely localized near the surface. The phase separation is indirectly confirmed by resistance measurements of the layers and ab initio calculations of the doped ITO electronic structure. The results obtained give hope for the creation of transparent superconducting films with critical temperatures of about 10 K.

Multiscale exploration of Ti-Nb-Zr-based alloys for enhanced bioimplant performance

Beta-titanium alloys (β-Ti alloys) with low elastic modulus are metallic materials of great technological interest for high-performance bioimplants. This study employs a comprehensive multiscale approach to investigate alloys from the Ti-Nb-Zr-Sn system, exhibiting desired bioimplant properties such as low elastic modulus and high β-phase stability. The multiscale strategy encompasses electronic structure calculations, integrating them with device simulations through a coupling of calculation of phase diagrams, density functional theory (DFT), machine learning (ML), and finite element analysis (FEA). Utilizing ML and DFT methodologies, we predict and analyze the elastic and electronic properties of the optimized ternary and quaternary alloys. DFT calculations point to elevated β-phase stability compared to omega-phase, suggesting a potential formation of orthorhombic martensite in the Ti-22Zr-11 Nb-4Sn (at%) alloy. Incorporating small amounts of Sn changes the nature of the bonds, resulting in structural and electronic stabilization of the beta-phase. FEA further validates the mechanical performance of the proposed alloys, demonstrating their potential compared to the well-established Ti-Nb-Ta-Zr (TNZT) alloy, a reference in the field. Our findings underscore the effectiveness of multiscale methodologies in advancing the understanding of alloy design for bioimplant applications. We conclude that this multiscale strategy not only elucidates the compositions of interest but also serves as a catalyst for innovation and progress in the field of bioimplantation.

Comprehensive Investigation of [formula omitted] and [formula omitted] Rare Earth-Based Scintillation Materials Using Density Functional Theory

In this paper, we investigate the structural, elastic, electronic, and optical properties of the new rare earth-based scintillation materials Rb2LuCl5 and Rb2PrCl5 using DFT calculations. The results show that both compounds are dynamically stable. Analysis of the elastic properties reveals that Rb2PrCl5 is more isotropic in its mechanical behavior, while Rb2LuCl5 exhibits a greater degree of anisotropy. Both Rb2LuCl5 and Rb2PrCl5 have direct band gaps (5.0698 and 4.7022 eV, respectively), according to electronic structure calculations. In terms of optical properties, both compounds exhibit higher transmittance and lower reflectance at lower energies. Calculated light yields show that under ideal conditions, Rb2LuCl5 can achieve a light yield of 78898 photons per MeV, while Rb2PrCl5 can reach a light yield of 85066 photons per MeV. This study provides valuable insights into the properties of these new rare earth-based scintillation materials, which can contribute to the development and optimization of improved scintillation detectors.

DFT study of the electronic, optical and elastic properties of Cu2-xAgxMgSnS4 (x=0, 0.5, 1, 1.5, 2) alloys using TB-mBJ+U potential

In this study, we have conducted first-principles computations on the promising photovoltaic materials Cu2-xAgxMgSnS4 (x=0, 0.5, 1, 1.5, 2). To determine the electronic characteristics of Cu2-xAgxMgSnS4(x=0, 0.5, 1, 1.5, 2) in kesterite and stannite phases, we have used the Wien2k code based on density functional theory with the generalised gradient approximation (GGA) and modified Becke-Johnson (TB-mBJ) exchange potential. The results obtained by TB-mBJ likewise fall short of the experimental findings, like GGA and LDA. To get a comparable bandgap value with the experimental results, we have employed the TB-mBJ potential coupled with the Hubbard U correction (TB-mBJ + U), resulting in a more accurate representation of the pd hybridization. Electronic structure calculation reveals Cu2-xAgxMgSnS4(x=0, 0.5, 1, 1.5, 2) materials as direct bandgap semiconductors, with band gaps ranging from 1.477 eV to 2.38 eV. The computed elastic constants confirm the mechanical stability of all materials. Additionally, we explored optical properties essential for their potential as absorber layers in photovoltaic applications, such as the imaginary and real components of the dielectric function, absorption coefficient, refractive index, reflectivity, and extinction coefficient. These predicted parameters provide valuable insights for researchers, facilitating further investigations into the photovoltaic potential of Cu2-xAgxMgSnS4 materials.