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At least 883 records · Page 49

Approximate spin projected spin-unrestricted density functional theory method: Application to diradical character dependences of second hyperpolarizabilities

We develop a novel method for the calculation and the analysis of the one-electron reduced densities in open-shell molecular systems using the natural orbitals and approximate spin projected occupation numbers obtained from broken symmetry (BS), i.e., spin-unrestricted (U), density functional theory (DFT) calculations. The performance of this approximate spin projection (ASP) scheme is examined for the diradical character dependence of the second hyperpolarizability (γ) using several exchange-correlation functionals, i.e., hybrid and long-range corrected UDFT schemes. It is found that the ASP-LC-UBLYP method with a range separating parameter μ = 0.47 reproduces semi-quantitatively the strongly-correlated [UCCSD(T)] result for p-quinodimethane, i.e., the γ variation as a function of the diradical character.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Electronic structure and atomic level complexity in Al 0.5 TiZrPdCuNi high-entropy alloy in glass phase

We present that high entropy alloys (HEAs), or concentrated solid solution alloys, are chemically complex metallic solid solutions in which five or more elements occupy the same crystallographic lattice sites with nearly equal compositions. The high degree of chemical disorder gives rise to considerable local lattice distortions, atomic-level stresses, and complex electronic structure, resulting in interesting properties. We calculated the electronic structure and the atomic-level stresses of Al x Ti y Zr y Pd y Cu y Ni y , x = 0.5, y = 1 (Al 0.5 TiZrPdCuNi) HEA in the glassy phase using the density functional theory (DFT) approach. We also briefly discuss the electronic structure in its crystalline phase. Whereas it has been reported recently that the crystalline phase of this HEA is obtained as a metastable phase during the crystallization of a glassy phase, the crystalline phase was found to be unstable at T = 0 in the DFT calculation. For this reason, we focus mainly on the glassy phase in this work. Lastly, the importance of charge transfer among elements on the atomic-level pressure and the role for atomic-level stresses to characterize the electronic and structural heterogeneity are discussed.

36 MATERIALS SCIENCE↗

Hygroscopic La[B{sub 5}O{sub 8}(OH)]NO{sub 3}·2H{sub 2}O: Insight into the evolution of borate fundamental building blocks

Borates have exceptionally diverse fundamental building blocks (FBBs), but factors controlling the formation of borate FBBs are poorly understood. The title compound La[B{sub 5}O{sub 8}(OH)]NO{sub 3}·2H{sub 2}O crystallizes in the space group P2{sub 1}/n with a=6.5396(12) Å, b=15.550(3) Å, c=10.6719(19) Å, β=90.44(1)° and Z=4 at 173(2) K. Its structure has been refined from single-crystal X-ray diffraction data to R{sub 1}=0.049 (for 2465) and wR{sub 2}=0.173 (for 2459 I>2σ(I)). This structure analysis and first-principles calculations show that the change of the FBB from 3Δ2□ in the title compound to 2Δ3□ in La[B{sub 5}O{sub 8}(OH)(H{sub 2}O)]NO{sub 3}·2H{sub 2}O is accompanied by a rotation of the NO{sub 3} group. FTIR, Rietveld and thermal analysis results show that the hygroscopic title compound is partially changed to La[B{sub 5}O{sub 8}(OH)(H{sub 2}O)]NO{sub 3}·2H{sub 2}O, with the conversion of [BO{sub 3}] to [BO{sub 3}(H{sub 2}O)] by water absorption. - Graphical abstract: The change of fundamental building blocks from La[B{sub 5}O{sub 8}(OH)]NO{sub 3}·2H{sub 2}O to La[B{sub 5}O{sub 8}(OH)(H{sub 2}O)]NO{sub 3}·2H{sub 2}O is accompanied by a rotation of the NO{sub 3} group . Display Omitted - Highlights: • Synthesis of a new hydrous lanthanum polyborate nitrate. • Single-crystal XRD structure with the 3Δ2⎕ FBB and an oriented NO{sub 3} group. • DFT calculations locate the H positions in three lanthanide polyborate nitrates. • Rietveld, FTIR and DFT results show hygroscopicity changes the FBBs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Anticorrelation between Surface and Subsurface Point Defects and the Impact on the Redox Chemistry of TiO2(110)

Using combination of STM, DFT and SIMS, we explored the interplay and relative impact of surface vs. subsurface defects on the surface chemistry of rutile TiO2. STM results show that surface O vacancies (VO’s) are virtually absent in the vicinity of positively-charged subsurface point-defects. This observation is consistent with DFT calculations of impact of subsurface defect proximity on VO formation energy. To monitor the influence of such lateral anticorrelation on surface redox chemistry, a test reaction of the dissociative adsorption of O2 is employed, which is observed to be suppressed around them. DFT results attribute this to a perceived absence of the intrinsic (Ti) (and likely extrinsic) interstitials in the nearest subsurface layer beneath “inhibited” areas. We also postulate that the entire nearest subsurface region could be voided of any charged point-defects, whereas prevalent VO’s are largely responsible for mediation of the redox chemistry at reduced TiO2(110) surface.

Environmental Molecular Sciences Laboratory↗

Spectroscopic Insight on Neodymium Solvation in Lithium Borohydride-Supported Electrolyte

Borohydride-based electrolytes have recently emerged as promising media for the electrodeposition of electropositive metals, including rare earth (RE) elements. While the presence of supporting alkali metal cations and RE counteranions provides essential electrochemical conductivity for achieving fast metal electrodeposition, interactions between the host ligand and solvated neodymium (Nd) complexes remain unclear. This study provides insights into the coordination structure of a concentrated and directly solvated Nd salt in a lithium borohydride-supported electrolyte. Our spectroscopic results indicate that the RE coordination environment is significantly influenced by the solvation mechanism, which can vary between metathesis and complexation pathways, primarily dictated by stoichiometric factors. Under dilute conditions, nearly complete metathesis of anions leads to a high coordination number for the host ligand (borohydride), consistent with the previously reported solvated Nd speciation in chlorine-free electrolytes. In contrast, concentrated dissolution of the Nd salt in the supported electrolyte is dominated by a complexation pathway featuring a Li-ion-paired complex with a low coordination number of the host ligand. Density functional theory (DFT) calculations indicated that the observed blue shift in the borohydride vibration was the result of an increase in electron density drawn into the terminal B–H interbond region from the hydride as the coordination changed from Li to Nd. In conjunction with DFT results, vibrational analyses allowed correlation of the experimental shifts associated with changes in Nd ligation and coordination spheres, further consolidating the prevalence of highly chloride-coordinated species under concentrated conditions. In conclusion, the outcomes of this work illuminate the distinctive and heterogeneous coordination structures that the electroactive RE species can adopt at high concentrations in lithium borohydride-supported electrolytes, as a key step to comprehend the reported metal electrodeposition performance in these media.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reducing Reaction Temperature, Steam Requirements, and Coke Formation During Methane Steam Reforming Using Electric Fields: A Microkinetic Modeling and Experimental Study

In this study, we approach several common problems with the Ni-catalyzed methane steam reformation reaction (MSR) using a two-pronged approach combining density functional theory (DFT) calculations with experimental work. Specifically, we look at the deactivation of a Ni catalyst due to coke formation, its high operating temperature requirements, and the high steam-to-methane (H 2 O/CH 4 ) ratio needed for proper MSR operation. A DFT-based microkinetic model was developed in the presence and absence of electric fields and the results were compared with experimental results. The microkinetic model shows that under various electric fields, the most favorable MSR mechanism changed slightly. It also shows that the presence of a positive electric field decreases the surface coverage of carbon, increases the water coverage, accelerates the rate-limiting step of the C-H bond cleavage in methane, and increases the desorption rates of the syngas product (CO + H 2 ) during MSR. Consequently, for a given methane conversion, a positive electric field allows for significantly lower H 2 O/CH 4 ratio and operating temperatures as compared to systems without an electric field. These findings correspond well with experimental tests under a variety of operating conditions. In addition, improvement in the catalytic activity due to the presence of a positive electric field remained significant even at industrially relevant applied pressures improving the hydrogen yield greatly. Overall, we find that an applied electric field can play a significant role in improving the catalytic activity of heterogeneous reactions. Here, this information can guide the design of heterogeneous reactions in the presence of an electric field. By utilizing the electric field generated by various renewable energy sources, electric field assisted heterogeneous reactions can open up a paradigm in future energy research.

03 NATURAL GAS↗

Ir 6 In 32 S 21 , a polar, metal-rich semiconducting subchalcogenide

Subchalcogenides are uncommon, and their chemical bonding results from an interplay between metal–metal and metal–chalcogenide interactions. Herein, we present Ir 6 In 32 S 21 , a novel semiconducting subchalcogenide compound that crystallizes in a new structure type in the polar P31m space group, with unit cell parameters a = 13.9378(12) Å, c = 8.2316(8) Å, α = β = 90°, γ = 120°. The compound has a large band gap of 1.48(2) eV, and photoemission and Kelvin probe measurements corroborate this semiconducting behavior with a valence band maximum (VBM) of –4.95(5) eV, conduction band minimum of –3.47(5) eV, and a photoresponse shift of the Fermi level by ~0.2 eV in the presence of white light. X-ray absorption spectroscopy shows absorption edges for In and Ir do not indicate clear oxidation states, suggesting that the numerous coordination environments of Ir 6 In 32 S 21 make such assignments ambiguous. Electronic structure calculations confirm the semiconducting character with a nearly direct band gap, and electron localization function (ELF) analysis suggests that the origin of the gap is the result of electron transfer from the In atoms to the S 3p and Ir 5d orbitals. DFT calculations indicate that the average hole effective masses near the VBM (1.19m e ) are substantially smaller than the average electron masses near the CBM (2.51m e ), an unusual feature for most semiconductors. The crystal and electronic structure of Ir 6 In 32 S 21 , along with spectroscopic data, suggest that it is neither a true intermetallic nor a classical semiconductor, but somewhere in between those two extremes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Equation of state for Hf, Ta, W, Re, Os, Ir, Pt, and Au to multi-terapascal pressures from density-functional theory

We present the zero-temperature equation of state (pressure dependence of compression) and phase stability predictions for the 5d-transition metals obtained from all-electron density-functional theory (DFT) calculations. The results compare favorably with experiments but extend beyond current experimental capabilities to 10 TPa. Our study reveals phase changes that are explained from the calculated electronic structure. The cubic face-centered and body-centered structures (fcc and bcc), together with two-, three-, and four-layered hexagonal structures, play major roles under compression. The results’ dependence on the electron exchange and correlation in the DFT approach is investigated, and it is shown that the impact of the choice, while significant at lower pressures, diminishes in the terapascal regime. We further illustrate that the normal parabolic trends in atomic volume and bulk modulus with atomic number, due to the occupation of bonding and anti-bonding 5d states, break down at TPa pressures, suggesting drastically different chemical bonding at these extreme conditions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

BCM polytype structures from DFT - Data and Resources

This dataset contains structure files and results of density functional theory (DFT) calculations for the 12R (ground state) and 10H (metastable at ambient temperature) polytypes of BaCe0.25Mn0.75O3 (BCM). Starting from the experimentally determined average crystal structures, the structures were generated by sampling of the magnetic (12R and 10H) and atomic (10H) configurations based on DFT energies.

08 HYDROGEN↗

Towards Quantum-Chemical Level Calculations of SARS-CoV-2 Spike Protein Variants of Concern by First Principles Density Functional Theory

The spike protein (S-protein) is a crucial part of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), with its many domains responsible for binding, fusion, and host cell entry. In this review we use the density functional theory (DFT) calculations to analyze the atomic-scale interactions and investigate the consequences of mutations in S-protein domains. We specifically describe the key amino acids and functions of each domain, which are essential for structural stability as well as recognition and fusion processes with the host cell; in addition, we speculate on how mutations affect these properties. Such unprecedented large-scale ab initio calculations, with up to 5000 atoms in the system, are based on the novel concept of amino acid–amino acid-bond pair unit (AABPU) that allows for an alternative description of proteins, providing valuable information on partial charge, interatomic bonding and hydrogen bond (HB) formation. In general, our results show that the S-protein mutations for different variants foster an increased positive partial charge, alter the interatomic interactions, and disrupt the HB networks. We conclude by outlining a roadmap for future computational research of biomolecular virus-related systems.

60 APPLIED LIFE SCIENCES↗

Atomic Orbital Energy Matching vs Overlap in Actinide-Ligand Dative Bonding

Prebonding conditions and dative bond formation in actinide(IV)hexachloride complexes with U, Np, and Pu are studied by density functional theory (DFT) calculations, focusing on the interplay of atomic orbital (AO) overlap and AO energy matching in the formation of molecular orbitals (MOs) and the subsequent identification of dative bonds. The extent of donation is tracked via population analysis, MO localization, and bond-order criteria. DFT Fock matrices are used to setup models in which varying numbers of valence AOs interact to form dative bonds. The results confirm, among other effects, a contribution to metal−ligand covalency from the actinide (An) 6p shell. Better matching of An(5f) and Cl(3p) energies occurs as the An(5f) level stabilizes with increasing An effective nuclear charge. A near-degeneracy occurs in the case of the α-spin orbitals of the Pu system, but it is inconsequential. Altogether, better AO energy matching for An(5f) and Cl(3p) along the series U, Np, Pu is counter-balanced by decreasing AO overlap and decreasing availability of 5f acceptor orbitals, leading to similar bond orders and extents of donation in the three systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Improved pseudopotential transferability for magnetic and electronic properties of binary manganese oxides from DFT + U + J calculations

In this work, we employ the fully anisotropic DFT+U+J approach with the PBEsol functional to investigate ground-state magnetic and electronic properties of bulk binary manganese oxides: MnO, Mn 3 O 4 , α-Mn 2 O 3 , and β-MnO 2 , in order of increasing Mn valence. The computed crystal structures, noncollinear magnetic ground states, and corresponding electronic structures are in good agreement with the experimental data and hybrid functional calculations available in the literature. We take into account the nonlinear core-valence interaction in our Mn pseudopotential designed by ourselves, as it has been proven to be important for transition-metal systems. Although the Hubbard U term is capable by itself of opening a band gap, the explicitly defined exchange parameter J plays an important role in improving the detailed electronic and noncollinear magnetic structure profiles. Appropriate band gaps are obtained with U values smaller than those used in previously reported calculations. Our results suggest that pseudopotential design together with DFT+U+J enables the acquisition of accurate properties of complex magnetic systems using a nonhybrid density functional.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Kinetics of low-temperature methane activation on IrO 2 (1 1 0): Role of local surface hydroxide species

The ability of the IrO 2 (1 1 0) surface to promote CH 4 activation at low temperatures (~150 K) suggests possibilities for developing IrO 2 -based catalysts to selectively convert light alkanes to high-value chemicals. In this study, we present experimental results and microkinetic simulations, based on density functional theory (DFT) calculations, of temperature programmed reaction spectra (TPRS) obtained for CH 4 σ-complexes adsorbed on IrO 2 (1 1 0), and focus on clarifying how surface OH groups modify the branching between CH 4 desorption, activation and subsequent reactions during TPRS. Our DFT results predict that surface OH groups strongly destabilize CH 4 σ-complexes on IrO 2 (1 1 0) in addition to deactivating surface O-atoms that are needed to achieve CH 4 activation at low temperature. We demonstrate that a microkinetic model that incorporates the influence of surface OH groups on the CH 4 binding and reactivity reproduces experimental TPRS results which show that adsorbed CH 4 σ-complexes preferentially dissociate at low CH 4 coverage, but that an increasing fraction of the adsorbed CH 4 desorbs at low temperature (~120 K) with increasing initial CH 4 or H coverage. The simulations reveal that low-temperature CH4 desorption during TPRS arises primarily from CH 4 σ-complexes that are kinetically-trapped between adjacent surface OH groups, and are thus destabilized and unable to access reactive O-atoms. In addition, when the effect of adjacent OH groups is incorporated we find that the PBE-D3 functional incorporating dispersion provides CH 4 binding energies that agree more closely with that obtained from the TPRS experiments. Overall, our results demonstrate that the local effect of adjacent OH groups must be incorporated into any microkinetic models to properly capture the selectivity between extensive and partial oxidation in alkane conversion on IrO 2 (1 1 0) under reaction conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Prediction of organic homolytic bond dissociation enthalpies at near chemical accuracy with sub-second computational cost

Bond dissociation enthalpies (BDEs) of organic molecules play a fundamental role in determining chemical reactivity and selectivity. However, BDE computations at sufficiently high levels of quantum mechanical theory require substantial computing resources. In this paper, we develop a machine learning model capable of accurately predicting BDEs for organic molecules in a fraction of a second. We perform automated density functional theory (DFT) calculations at the M06-2X/def2-TZVP level of theory for 42,577 small organic molecules, resulting in 290,664 BDEs. A graph neural network trained on a subset of these results achieves a mean absolute error of 0.58 kcal mol-1 (vs DFT) for BDEs of unseen molecules. We further demonstrate the model on two applications: first, we rapidly and accurately predict major sites of hydrogen abstraction in the metabolism of drug-like molecules, and second, we determine the dominant molecular fragmentation pathways during soot formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structures and stabilities of alkaline earth metal peroxides XO2 (X=Ca, Be, Mg) studied by a genetic algorithm

The structures and stabilities of alkaline earth metal peroxides XO2 (X = Ca, Be, Mg) were studied using an adaptive genetic algorithm (GA) for global structure optimization in combination with first-principles calculations. From the adaptive GA search, we obtained an orthorhombic structure for CaO2 with 12 atoms in the unit cell, which is energetically more favorable than the previously proposed structures. Reaction energy of the decomposition CaO2 → CaO + 1/2O2 determined by density functional theory (DFT) calculation shows that this orthorhombic calcium peroxide structure is thermodynamically stable. The simulated X-ray diffraction (XRD) pattern using our predicted structure is in excellent agreement with experimental data. We also show that crystal phase BeO2 is unlikely to exist under normal conditions. MgO2 has a cubic pyrite structure, but it is not stable against decomposition: MgO2 → MgO + 1/2O2.

36 MATERIALS SCIENCE↗

Pb-Apatite Framework as a Generator of Novel Flat-Band CuO-Based Physics

Based upon density functional theory (DFT) calculations, we present the basic electronic structure of CuPb 9 (PO 4 ) 6 O (Cu-doped lead apatite, aka LK-99), in two scenarios: (1) where the structure is constrained to the P3 symmetry and (2) where no symmetry is imposed. At the DFT level, the former is predicted to be metallic while the latter is found to be a charge-transfer insulator. In both cases the filling of these states is nominally d 9 , consistent with the standard Cu 2+ valence state, and Cu with a local magnetic moment of order 0.7 μ B . In the metallic case we find these states to be unusually flat (∼0.2 eV dispersion), giving a very high density of electronic states (DOS) at the Fermi level that we argue can be a host for novel electronic physics. The flatness of the bands is the likely origin of symmetry-lowering gapping possibilities that would remove the spectral weight from E F . Motivated by some initial experimental observations of metallic or semiconducting behavior, we propose that disorder (likely structural) is responsible for closing the gap. Here, we consider a variety of possibilities that could possibly close the charge-transfer gap but limit consideration to kinds of disorder that preserve electron count. Of the possible kinds we considered (spin disorder, O populating vacancy sites, and Cu on less energetically favorable Pb sites), the local Cu moment, and consequently the charge-transfer gap, remains robust. We conclude that disorder responsible for metallic behavior entails some kind of doping where the electron count changes. Further, we claim that the emergence of the flat bands should be due to weak wave function overlap between the orbitals on Cu and O sites, owing to the directional character of the constituent orbitals. Therefore, finding an appropriate host structure for minimizing hybridization between Cu and O while allowing them to still weakly interact should be a promising route for generating flat bands at E F which can lead to interesting electronic phenomena, regardless of whether LK-99 is a superconductor.

36 MATERIALS SCIENCE↗

Synthesis, Electronic Structure, and Reactivity of a Planar Four‐Coordinate, Cobalt–Imido Complex

Abstract A four‐coordinate cobalt–imido complex, ( t Bu mPNP)Co=NMes ( t Bu mPNP=modified PNP pincer ligand) has been synthesized from addition of 2,4,6‐trimethylphenylazide (Mes–N 3 ) to the corresponding dinitrogen complex. The solid‐state structure determined by X‐ray diffraction established a rare, idealized planar geometry with a Co=N bond distance of 1.716(2) Å. Magnetic measurements revealed an S =1 ground state with CAS‐SCF calculations supporting radical character on the imide nitrogen. Thermolysis of the cobalt–imido compound induced selective insertion of the imido group into a Co−P bond and yielded a three‐coordinate cobalt complex with a distorted T‐shaped geometry. Transition state analysis conducted with DFT calculations established the thermodynamic stability of the P–N coupled product and provided insight into the exclusive selectivity.

Park, Yoonsu↗

Radiation Effects on Uranyl Tetrachloro Coordination Compounds: Impact of Lattice Water

Nuclear materials, such as uranium-bearing solids, are exposed to high levels of ionizing radiation throughout the nuclear fuel cycle; thus, it is important to develop a molecular-level understanding of how these materials behave and degrade in the presence of gamma (γ) irradiation. In the current study, three U(VI) tetrachloride complexes, M 2 [UO 2 Cl 4 ]·xH 2 O (where M = K + , Rb + , or Cs + and x = 0 or 2), and their respective chloride salts were exposed to 1–50 kGy of γ radiation using a 60 Co source. Irradiated materials were evaluated by using electron paramagnetic resonance (EPR) and Raman spectroscopy and were further explored by using density functional theory (DFT) methods. EPR spectra of the irradiated materials suggest the formation of a Cl-based radical for both the alkali salts and the uranyl tetrachloride compounds, and DFT calculations provide evidence that the Cl 2 –• radical is formed within these materials. The presence of water in the K + and Rb + compounds leads to additional spectroscopic signatures that could be traced back to water radiolysis and the formation of peroxide and superoxide species. DFT results support the formation of HO 2 • in the lattice and potentially the formation of a [UO 2 Cl 3 (O 2 )] 3– species, highlighting the impact of water within the hydrated material to alter U(VI) speciation by radiolysis.

36 MATERIALS SCIENCE↗