Relativistic Density Research Articles

Topological material in the III–V family: Heteroepitaxial InBi on InAs

InBi(001) is formed epitaxially on InAs(111)-A by depositing Bi onto an In-rich surface. Angle-resolved photoemission measurements reveal topological electronic surface states, close to the M¯ high symmetry point. This demonstrates a heteroepitaxial system entirely in the III–V family with topological electronic properties. InBi shows coexistence of Bi and In surface terminations, in contradiction with other III–V materials. For the Bi termination, the study gives a consistent physical picture of the topological surface electronic structure of InBi(001) terminated by a Bi bilayer rather than a surface formed by splitting to a Bi monolayer termination. Theoretical calculations based on relativistic density functional theory and the one-step model of photoemission clarify the relationship between the InBi(001) surface termination and the topological surface states, supporting a predominant role of the Bi bilayer termination. Furthermore, a tight-binding model based on this Bi bilayer termination with only Bi–Bi hopping terms, and no Bi–In interaction, gives a deeper insight into the spin texture. Published by the American Physical Society 2024

Periodic Bonding Behaviors of Actinide Atoms (An = Th-Cm) with Negatively Curved Nanographene.

The nanographene with negative curvature has been extensively studied due to its interesting properties and potential applications. In the present work, we have performed all-electron scalar relativistic density functional theory (DFT) calculations to understand the periodic interaction mechanisms of actinide atoms (An = Th, Cm) with the TB8C nanographene. The encapsulated complexes (An@TB8C) were formed due to the octagonal vacancy in the TB8C nanographene. TB8C shows fairly high affinity toward An atoms, especially for Th and Pa. AIMD simulations further confirmed the effective trapping of An atom with TB8C. The partial covalent characters of An-C bonds in An@TB8C were revealed through various bond analysis methods. The 6d electrons of An play an important role in the participation of chemical bonds. The delocalization index (DI) is proposed as a useful descriptor in the study of bond strength involving the actinides. Electronic absorption spectra were simulated for further identification in the experiments. The current work has expanded the potential molecular properties and applications of nanographene.

Superheavy magic nuclei: Ground-state properties, bubble structure and α-decay chains

A systematic investigation of superheavy nuclei in the isotopic chains of proton numbers Z=106, 114, 120, and 126 together with isotonic chains of neutron numbers N=162, 172, and 184 is presented in the theoretical framework of relativistic mean-field density functionals based on density-dependent meson-nucleon couplings. Ground-state properties, including binding energy, shape, deformation, density profile, and radius, are estimated to provide compelling evidence of magicity in these even-even nuclei, aligning with the concept of the ‘island of stability.’ The analysis reveals central depletion in the charge density, indicating a bubble-like structure, primarily attributed to the substantial repulsive Coulomb field and the influence of higher l-states. A thorough examination of potential decay modes, employing various semi-empirical formulas, is presented. The probable α-decay chains are evaluated, demonstrating excellent agreement with available experimental data.

Elucidate the non-relativistic and relativistic energy density functional from momentum space to coordinate space within local density approximation

Elucidate the non-relativistic and relativistic energy density functional from momentum space to coordinate space within local density approximation

A pH switchable hydrophilic fluorescent BODIPY sodium disulfonate for Fe3+ multicolor detection: Experimental and DFT studies

BODIPY-based chemosensors are widely used owing to merits like good selectivity, high fluorescence quantum yield, and excellent optical stability. As such, a pH-switchable hydrophilic fluorescent probe, BODIPY-PY-(SO3Na)2, was developed for detection of Fe3+ ion in aqueous solutions. BODIPY-PY-(SO3Na)2 revealed strong fluorescence intensity and was responsive to pH value in the range of 6.59–1.96. Additionally, BODIPY-PY-(SO3Na)2 showed good selectivity and sensitivity towards Fe3+. A good linear relationship for Fe3+ detection was obtained from 0.0 μM to 50.0 μM with low detecting limit of 6.34 nM at pH 6.59 and 2.36 nM at pH 4.32, respectively. The response to pH and detection of Fe3+ induced obvious multicolor changes. BODIPY-PY-(SO3Na)2 can also be utilized to quantitatively detect Fe3+ in real water sample. Different mechanisms of Fe3+ detection at investigated pH values were unraveled through relativistic density functional theory (DFT) calculations in BODIPY-PY-(SO3Na)2 and experiments of coexisting cations, anions and molecules. These results enabled us to gain a deeper understanding of the interactions between BODIPY-PY-(SO3Na)2 and Fe3+ and provide valuable fundamental information for design of efficient multicolor chemosensors for Fe3+ as well.

Reactivity of Zinc Fingers in Oxidizing Environments: Insight from Molecular Models Through Activation Strain Analysis.

The reactivity of Zn2+ tetrahedral complexes with H2O2 was investigated in silico, as a first step in their disruption process. The substrates were chosen to represent the cores of three different zinc finger protein motifs, i. e., a Zn2+ ion coordinated to four cysteines (CCCC), to three cysteines and one histidine (CCCH), and to two cysteines and two histidines (CCHH). The cysteine and histidine ligands were further simplified to methyl thiolate and imidazole, respectively. H2O2 was chosen as an oxidizing agent due to its biological role as a metabolic product and species involved in signaling processes. The mechanism of oxidation of a coordinated cysteinate to sulfenate-κS and the trends for the different substrates were rationalized through activation strain analysis and energy decomposition analysis in the framework of scalar relativistic Density Functional Theory (DFT) calculations at ZORA-M06/TZ2P ae // ZORA-BLYP-D3(BJ)/TZ2P. CCCC is oxidized most easily, an outcome explained considering both electrostatic and orbital interactions. The isomerization to sulfenate-κO was attempted to assess whether this step may affect the ligand dissociation; however, it was found to introduce a kinetic barrier without improving the energetics of the dissociation. Lastly, ligand exchange with free thiolates and selenolates was investigated as a trigger for ligand dissociation, possibly leading to metal ejection; molecular docking simulations also support this hypothesis.

Electric field gradients at the nuclei from all-electron four-component relativistic density functional theory using Gaussian-type orbitals

Electric field gradients at the nuclei from all-electron four-component relativistic density functional theory using Gaussian-type orbitals

Unified insights: Relativistic density functional theory for proton resonance, emission, and proton-rich exotic nuclei

Unified insights: Relativistic density functional theory for proton resonance, emission, and proton-rich exotic nuclei

Coexistence of pure octupole shapes in the superheavy nucleus 286No

The shape of 286No is investigated with the relativistic density functional theory on a three-dimensional lattice space without any symmetry restriction in a microscopic and self-consistent way. It is found that the ground state of 286No has a pure non-axial octupole shape and coexists with a tetrahedral isomeric state. The energy difference between the two states is only 0.12 MeV, and they are separated by a potential barrier of about 0.5 MeV. The occurrence of the octupole correlations is analyzed with the evolution of the single-particle levels near the Fermi surface driven by the octupole deformations.

Observing the Role of Electron Delocalization in Electronic Transport by Incorporating Actinides into Ligated Metal-Chalcogenide Superatoms.

Since delocalization of electronic states is a prerequisite for exerting unique electron transport properties, early actinides (An) with highly delocalized 5f/6d orbitals are natural candidates. However, given the experimental difficulties of such radioactive compounds and the complex relativistic effects in theoretical studies, understanding the electronic structure and bonding of actinides is underdeveloped on the periodic table. A further challenge is the very complicated electronic structures encountered in the confinement of actinides, as vividly illustrated by the weakly radioactive Th(Thorium)-encapsulated metal chalcogenide clusters, Th@Co6Te8L6 (L = PH3, PMe3, PEt3). Here we report the electronic structure and the electron transport properties of the Th@Co6Te8L6 clusters and compare them with those of the hollow Co6Te8L6 clusters using the nonequilibrium Green's function combined with relativistic density functional theory (NEGF-DFT). We found that the equilibrium conductance in Th@Co6Te8(PH3)6 (0.76 G0) has been greatly improved over that in Co6Te8(PH3)6 (0.03 G0), which has also been verified under an applied different bias voltage. The covalent bonding character between 6d (Th) and 3d (Co) atomic orbitals resulting from steric confinement is the source of the performance enhancement and a most important factor governing the accessibility of such 5f/6d orbitals. The results are of significance to the rapidly developing field of molecular nanoelectronics.

Correlation between neutrinoless double-β decay and double Gamow-Teller transitions

The neutrinoless double-β (0νββ) decay and the double Gamow-Teller (DGT) transition are investigated with the state-of-the-art Relativistic Configuration-interaction Density functional theory. A strong linear correlation between the nuclear matrix elements (NMEs) of the 0νββ decay and the DGT transition is demonstrated. This linear correlation is found to originate from the similarity of the leading-order term of the 0νββ-decay operator and the DGT-transition one, as revealed by expanding the 0νββ-decay operator in terms of the spherical harmonics. The present results provide a strong support to constrain the 0νββ-decay NMEs through the double charge-exchange reactions.

Theoretical study of the ability of symmetric and asymmetric N-donor ligands to separate Am(III) and Eu(III) and the bonding nature

In the reprocessing of spent nuclear fuel, nitrogen-donor extractants are more effective in separating actinides and lanthanides. In this article, a series of heterocyclic N-donor ligands with different backbones and different side chain substituents are systematically investigated to analyze their extraction selectivity and complexation abilities for Am(Ⅲ) and Eu(Ⅲ) by using scalar relativistic density functional theory (DFT). Through the analysis of geometric structures and bond properties of the complexes by means of the NBO and QTAIM methods, it was observed that the coordination ability of the N-donor ligand with Am(Ⅲ) was stronger than with Eu(Ⅲ). Thermodynamic analysis showed that these ligands have good extraction ability and separation performance for Am(III) and Eu(III), the backbone and side chain substituents of the ligands and also the organic solvents have significant influences on the extraction selectivity of the ligands for Am(III) and Eu(III) ions. This work provides some theoretical insights for the design of N-donor extractants with good separation performance for lanthanides and actinides.

A relativistic DFT study of small-molecule activation facilitated by actinocenes (An(η8-C8H8)2)

The scarcity and radioactivity of actinides have made it very difficult to study actinocene and other actinide-containing complexes experimentally. Hence, theoretical studies of these complexes can offer significant direction in the enlightenment of difficult-to-obtain experimental data. Keeping in mind, actinocene (An(COT)2, An = Th, Pa, U, Np, Pu, Am, Cm) with D8h symmetry has been investigated in the present study. Under D8h symmetry, the structural parameters of optimized sandwich compounds are found to be in concurrence with the experimental data. This study extensively examines the experimentally characterized actinocene for their capability to activate small molecules (Y = CO, and N2) through relativistic density functional theory (DFT) analysis. After forming a complex with CO, and N2, D8h symmetry of An(COT)2 gets distorted resulting in the bending of both the COT rings. In all the [An(COT)2Y] complexes, a covalent bond was realized between An and Y except [U(COT)2N2], [Np(COT)2N2], and [Pu(COT)2N2], where an ionic bond was observed between An and Y. Furthermore, the experimental inaccessible [An(COT)2Y] complexes were elucidated through thermodynamic computations along with the analyses of geometric, electronic properties and bonding analysis. [Pu(COT)2N2] adducts have the largest contribution of ΔEorb to total ΔEint among all the complexes suggesting that the Pu-N bond is dominated by orbital attractions and shows significant covalency.

Complexation of trivalent Eu and Am ions with phenanthroline-derived ligands tuned by rotating thiazole/oxazole substituents

The reprocessing of spent nuclear fuels is greatly challenging, as the current separation technique of lanthanide (Ln) and actinide (An) suffers too many difficulties. In this paper, selective ligands of phenanthroline derivatives modified by thiazole/oxazole were designed by relativistic density functional theory calculations. Their complexation of Eu3+ and Am3+ and the mechanism of selective separation were comprehensively examined. The spatial rotation against the CC bond between phenanthroline and thiazole/oxazole has access to six ligands. It is shown that Looo with oxazole substituents and their oxygens being opposite is the best electron donor for metal ions. The results of WBIs and MBO unravel that Am-L bond has more covalency than respective Eu-L bond. From topological analyses, it is found that these metal–ligand bonds are dominated by electrostatic interaction and largely of ionic bond character. Thermodynamically, all ligands prefer binding Eu3+ to Am3+.

On the geometry dependence of the nuclear magnetic resonance chemical shift of mercury in thiolate complexes: A relativistic density functional theory study.

Thiolate containing mercury(II) complexes of the general formula [Hg(SR) ] have been of great interest since the toxicity of mercury was recognized. 199Hg nuclear magnetic resonance spectroscopy (NMR) is a powerful tool for characterization of mercury complexes. In this work, the Hg shielding constants in a series of [Hg(SR) ] complexes are therefore investigated computationally with particular emphasis on their geometry dependence. Geometry optimizations and NMR chemical shift calculations are performed at the density functional theory (DFT) level with both the zeroth-order regular approximation (ZORA) and four-component relativistic methods. The four exchange-correlation (XC) functionals PBE0, PBE, B3LYP, and BLYP are used in combination with either Dyall's Gaussian-type (GTO) or Slater-type orbitals (STOs) basis sets. Comparing ZORA and four-component calculations, one observes that the calculated shielding constants for a given molecular geometry have a constant difference of 1070 ppm. This confirms that ZORA is an acceptable relativistic method to compute NMR chemical shifts. The combinations of four-component/PBE0/v3z and ZORA/PBE0/QZ4P are applied to explore the geometry dependence of the isotropic shielding. For a given coordination number, the distance between mercury and sulfur is the key factor affecting the shielding constant, while changes in bond and dihedral angles and even different side groups have relatively little impact.

Bis(acyl)phosphide Complexes of U(III)/U(IV): A Case of a Hidden Redox-Active Ligand.

The recently reported tris(bis(2,4,6-triisopropylbenzoyl)-phosphide)uranium (UIII(trippBAP)3, 2) complex (Inorg. Chem. 2022, 61 (32), 12508-12517) demonstrated a silent 31P NMR spectrum. This complex was described as a U(III) complex with an organic radical ligand fragment. Moreover, the EPR spectrum of 2 was indicative of an organic radical in the ligand framework complexed to uranium, in contrast to that of UIV(mesBAP)4, 1. Herein, with the help of relativistic density functional theory (DFT) calculations, the electronic structures of 1, 2, and U(mesBAP)3 (4) are examined in an effort to understand the unusual 31P NMR spectrum of 2. Results indicate the reduction of the carbonyl bonds and delocalization of the electrons over the ligands, indicative of U → L backbonding. Additionally, the reduced acyl carbons are found to exist as ketyl radicals [O═C• -] that are responsible for the silent 31P NMR spectra of 2. These findings demonstrate the redox noninnocent nature of BAP- in 2 and 4, causing uranium to exist in a formal oxidation state of +4.

Exploring the bonding and extraction separation effects of N donor ligands with different skeletons on Am(III) and Eu(III)

Designing ligands for effective separation of actinide(III)/lanthanide(III) is one of the key issues in the treatment of spent nuclear fuel. However, due to the chemical similarity of trivalent actinides and lanthanides, their separation faces a great challenge in the reprocessing of spent nuclear fuel. Nitrogen donor extractants are considered as promising reagents for separation of trivalent actinides and lanthanides. To the best of our knowledge, the pre-organized structure of the ligand has a strong influence on the extraction separation capacity. In this work, we designed four N-donor ligands (L1 and L2 with pyridine and bipyridine skeletons, respectively, and L3 and L4 both with phenanthroline skeletons) with different pre-organized structures and investigated their selective extraction for Am(III) and Eu(III) by using scalar relativistic density functional theory (DFT). The absolute minimum ESP values of these ligands and the higher HOMO level suggest that the ligand L2 may have a stronger affinity for Am(III)/Eu(III) ions than other ligands. The three average bond lengths of each complex indicate that the Am(III) and Eu(III) ions have larger bond lengths with N2 atoms than with N1 atoms. Various theoretical approaches have been used to evaluate the properties of the four ligands as well as the coordination structures, bonding properties and thermodynamic properties of the complexes of the four ligands with Am(III) and Eu(III). The WBIs, QTAIM, NBO, DOS and EDA analysis indicate that the metal–ligand bonds are mainly ionic in character, the Am-N bond has more covalency than the Eu-N bond because the Am 5f orbitals are more involved in bonding with ligand than Eu 4f orbitals. According to the extended transition state and natural orbital chemical valence theory (ETS-NOCV) analysis, electrons are obviously transferred from the lone pair of the ligand N atom to the hybrid s, d and f orbitals of the metal ion. The thermodynamic results show that the four ligands can coordinate well with the Am and Eu ions, and also have suitable separation capacity for Am and Eu. Among the four ligands, the L2 and L3 ligands have the strongest coordination ability for metals and the best extraction separation effect for Am and Eu. It can be seen that the bridging skeleton of the ligand and the number of N atoms on the five-membered ring and also different organic solvents have obvious effects on the extraction and separation capacity of the ligand. This study provides a theoretical basis for the efficient separation of Am(III)/Eu(III) by adjusting the preorganization level of ligands, and provides a theoretical basis for the design and screening of ligands by preorganization.

Dirac-Coulomb-Breit Molecular Mean-Field Exact-Two-Component Relativistic Equation-of-Motion Coupled-Cluster Theory.

We present a relativistic equation-of-motion coupled-cluster with single and double excitation formalism within the exact two-component framework (X2C-EOM-CCSD), where both scalar relativistic effects and spin-orbit coupling are variationally included at the reference level. Three different molecular mean-field treatments of relativistic corrections, including the one-electron, Dirac-Coulomb, and Dirac-Coulomb-Breit Hamiltonian, are considered in this work. Benchmark calculations include atomic excitations and fine-structure splittings arising from spin-orbit coupling. Comparison with experimental values and relativistic time-dependent density functional theory is also carried out. The computation of the oscillator strength using the relativistic X2C-EOM-CCSD approach allows for studies of spin-orbit-driven processes, such as the spontaneous phosphorescence lifetime.

Weak Bimetal Coupling-Assisted MN4 Catalyst for Enhanced Carbon Dioxide Reduction Reaction.

The design of multimetal catalysts holds immense significance for efficient CO2 capture and its conversion into economically valuable chemicals. Herein, heterobimetallic catalysts (MiMo)L were exploited for the CO2 reduction reactions (CO2RR) using relativistic density functional theory (DFT). The octadentate Pacman-like polypyrrolic ligand (H4L) accommodates two metal ions (Mo, W, Nd, and U) inside (Mi) and outside (Mo) its month, rendering a weak bimetal coupling-assisted MN4 catalytically active site. Adsorption reactions have access to energetically stable coordination modes of -OCO, -OOC, and -(OCO)2, where the donor atom(s) are marked in bold. Among all of the species, (UiMoo)L releases the most energy. Along CO2RR, it favors to produce CO. The high-efficiency CO2 reduction is attributed to the size matching of U with the ligand mouth and the effective manipulation of the electron density of both ligand and bimetals. The mechanism in which heterobimetals synergetically capture and reduce CO2 has been postulated. This establishes a reference in elaborating on the complicated heterogeneous catalysis.

Relativistic energy density functional from momentum space to coordinate space within a coherent density fluctuation model

In this theoretical study, we have derived a simplified analytical expression for the binding energy per nucleon as a function of density and isospin asymmetry within the relativistic mean-field model. We have generated a new parameterization for the density-dependent DD-ME2 parameter set using the Relativistic-Hartree-Bogoliubov approach. Moreover, this work attempts to revisit the prior polynomial fitting in Kumar A. et al. Phys. Rev. C, 103 (2021) 024305 for the non-linear NL3 force parameter to provide a simplified set of equations for the energy density functional which is used for calculating the surface properties of finite nuclei. The current study improves the existing fitting procedure by effectively proposing a simpler model that provides comparably precise results while lowering the computational expense. To study the surface properties of finite nuclei with these parameterizations, we have adopted the coherent density fluctuation model, which effectively translates the quantities of nuclear matter from momentum space to coordinate space at local density. The isospin properties, such as symmetry energy and its surface and volume components, slope parameter, finite nuclear incompressibility, and surface incompressibility for even-even nuclei, are calculated for different mass regions. Moreover, we have studied the effect of density, weight function, and choice of relativistic force parameters on the surface properties. The significance of this work will help to determine the properties of nuclei along the nuclear landscape and can facilitate an improved understanding of the island of stability, heavy-ion collision, and nucleosynthesis, among others.