Nuclear Density Functional Theory Research Articles

Signatures of shape phase transitions in krypton isotopes based on relativistic energy density functionals

Spectroscopic properties that characterize the shape phase transitions in krypton isotopes with the mass $A\approx80$ region are investigated within the framework of the nuclear density functional theory. Triaxial quadrupole constrained self-consistent mean-field calculations that employ relativistic energy density functionals and a pairing interaction are carried out for the even-even nuclei $^{76-86}$Kr. The spectroscopic properties are computed by solving the triaxial quadrupole collective Hamiltonian, with the ingredients, i.e., the deformation-dependent moments of inertia and mass parameters, and the collective potential, determined by using the SCMF solutions as microscopic inputs. Systematic behaviors of the SCMF potential energy surfaces, the corresponding low-energy spectra, electric quadrupole and monopole transition probabilities, and the fluctuations in the triaxial quadrupole deformations indicate evolution of the underlying nuclear structure as functions of the neutron number, that is characterized by a considerable degree of shape mixing. A special attention is paid to the transitional nucleus $^{82}$Kr, which has been recently identified experimentally as an empirical realization of the E(5) critical-point symmetry.

Octupole correlations in collective excitations of neutron-rich N≈56 nuclei

Octupole correlations in the low-energy collective states of neutron-rich nuclei with the neutron number $N\approx56$ are studied within the interacting boson model (IBM) that is based on the nuclear density functional theory. The constrained self-consistent mean-field (SCMF) calculations using a universal energy density functional and a pairing interaction provide the potential energy surfaces in terms of the axially-symmetric quadrupole and octupole deformations for the even-even nuclei $^{86-94}$Se, $^{88-96}$Kr, $^{90-98}$Sr, $^{92-100}$Zr, and $^{94-102}$Mo. The SCMF energy surface is then mapped onto the energy expectation value of a version of the IBM in the boson condensate state, which consists of the neutron and proton monopole $s$, quadrupole $d$, and octupole $f$ bosons. This procedure determines the strength parameters of the IBM Hamiltonian, which is used to compute relevant spectroscopic properties. At the SCMF level, no octupole deformed ground state is obtained, while the energy surface is generally soft in the octupole deformation at $N\approx56$. The predicted negative-parity yrast bands with the bandhead state $3^-_1$ weakly depend on $N$ and become lowest in energy at $N=56$ in each of the considered isotopic chains. The model further predicts finite electric octupole transition rates between the lowest negative- and the positive-parity ground-state bands.

High-Efficiency Fast-Radiative Blue-Emitting Perovskite Nanoplatelets and Their Formation Mechanisms.

High-efficiency blue perovskite emitters with fast fluorescence radiation are not only crucial to achieving high-quality displays but also highly desired for optical wireless communications and quantum information technologies. Here, we demonstrate the preparation of blue-emitting Eu3+-, Sb3+-, and Ba2+-induced CsPbBr3 nanoplatelets with narrow spectral widths. Among them, Sb3+-doped CsPbBr3 NPLs can reach a photoluminescence quantum yield of 95%, with a very short fluorescence lifetime of 1.48 ns and greatly reduced ligand dosage. Through nuclear magnetic resonance analysis and density functional theory calculations, we find that the dopant-ligand interaction and dopant-induced growth energy barrier decide the growth kinetics of doped nanoplatelets. These mechanisms offer a fresh route to controlling the dimension of nanoscale perovskite emitters and benefit the development of fast-radiative perovskite emitters.

Syn and Anti Metal Complexes of 24π Antiaromatic Bis(Dicarbonylrhodium(I))Dithiaamethyrin.

From the reaction of sterically less hindered tetrapropyl[24]dithiaamethyrin(1.0.0.1.0.0) 5, with [Rh(CO)2 Cl]2 , a unique anti form of the bis(dicarbonylrhodium(I)) complex (6-anti), where two rhodium ions are on the opposite faces of the macrocyclic ligand, was isolated for the first time in 12% yield along with the corresponding syn isomer (6-syn, 61% yield). These structures were characterized in detail by single-crystal X-ray structure analysis. Compound 6-syn exhibited a bowl-shaped structure with the two rhodium atoms separated by a distance of ∼4.5 Å. In contrast, 6-anti contained a wave-shaped macrocycle with a distance of ∼5.3 Å between the two rhodium atoms. Furthermore, the 1 H nuclear magnetic resonance spectra and density functional theory calculation results revealed that 6-anti had a stronger paratropic ring current and a more planar structure than 6-syn. The isolation of both 6-anti and 6-syn enabled detailed discussion of the structure-property relationship.

Evidence of Two-Source King Plot Nonlinearity in Spectroscopic Search for New Boson.

Optical precision spectroscopy of isotope shifts can be used to test for new forces beyond the standard model, and to determine basic properties of atomic nuclei. We measure isotope shifts on the highly forbidden ^{2}S_{1/2}→^{2}F_{7/2} octupole transition of trapped ^{168,170,172,174,176}Yb ions. When combined with previous measurements in Yb^{+} and very recent measurements in Yb, the data reveal a King plot nonlinearity of up to 240σ. The trends exhibited by experimental data are explained by nuclear density functional theory calculations with the Fayans functional. We also find, with 4.3σ confidence, that there is a second distinct source of nonlinearity, and discuss its possible origin.

Characterization of Chemisorbed Species and Active Adsorption Sites in Mg-Al Mixed Metal Oxides for High-Temperature CO2 Capture.

Mg–Al mixed metal oxides (MMOs), derived from the decomposition of layered double hydroxides (LDHs), have been purposed as adsorbents for CO2 capture of industrial plant emissions. To aid in the design and optimization of these materials for CO2 capture at 200 °C, we have used a combination of solid-state nuclear magnetic resonance (ssNMR) and density functional theory (DFT) to characterize the CO2 gas sorption products and determine the various sorption sites in Mg–Al MMOs. A comparison of the DFT cluster calculations with the observed 13C chemical shifts of the chemisorbed products indicates that mono- and bidentate carbonates are formed at the Mg–O sites with adjacent Al substitution of an Mg atom, while the bicarbonates are formed at Mg–OH sites without adjacent Al substitution. Quantitative 13C NMR shows an increase in the relative amount of strongly basic sites, where the monodentate carbonate product is formed, with increasing Al/Mg molar ratios in the MMOs. This detailed understanding of the various basic Mg–O sites presented in MMOs and the formation of the carbonate, bidentate carbonate, and bicarbonate chemisorbed species yields new insights into the mechanism of CO2 adsorption at 200 °C, which can further aid in the design and capture capacity optimization of the materials.

Microscopic analysis of induced nuclear fission dynamics

The dynamics of low-energy induced fission is explored using a consistent microscopic framework that combines the time-dependent generator coordinate method (TDGCM) and time-dependent nuclear density functional theory (TDDFT). While the former presents a fully quantum mechanical approach that describes the entire fission process as an adiabatic evolution of collective degrees of freedom, the latter models the dissipative dynamics of the final stage of fission by propagating the nucleons independently toward scission and beyond. By combining the two methods, based on the same nuclear energy density functional and pairing interaction, we perform an illustrative calculation of the charge distribution of yields and total kinetic energy for induced fission of $^{240}$Pu. For the saddle-to-scission phase a set of initial points for the TDDFT evolution is selected along an iso-energy curve beyond the outer fission barrier on the deformation energy surface, and the TDGCM is used to calculate the probability that the collective wave function reaches these points at different times. Fission observables are computed with both methods and compared with available data. The relative merits of including quantum fluctuations (TDGCM) and the one-body dissipation mechanism (TDDFT) are discussed.

β decay and evolution of low-lying structure in Ge and As nuclei

A simultaneous calculation for the shape evolution and the related spectroscopic properties of the low-lying states, and the $\beta$-decay properties in the even- and odd-mass Ge and As nuclei in the mass $A\approx70-80$ region, within the framework of the nuclear density functional theory and the particle-core coupling scheme, is presented. The constrained self-consistent mean-field calculations using a universal energy density functional (EDF) and a pairing interaction determines the interacting-boson Hamiltonian for the even-even core nuclei, and the essential ingredients of the particle-boson interactions for the odd-nucleon systems, and of the Gamow-Teller and Fermi transition operators. A rapid structural evolution from $\gamma$-soft oblate to prolate shapes, as well as the spherical-oblate shape coexistence around the neutron sub-shell closure $N=40$, is suggested to occur in the even-even Ge nuclei. The predicted low-energy spectra, electromagnetic transition rates, and $\beta$-decay $\log{ft}$ values are in a reasonable agreement with experiment. The predicted $\log{ft}$ values reflect the structures of the wave functions for the initial and final nuclei of $\beta$ decay, which are, to a large extent, determined by the microscopic input provided by the underlying EDF calculation.

Two-neutrino double- β decay in the mapped interacting boson model

A calculation of two-neutrino double-$\beta$ ($2\nu\beta\beta$) decay matrix elements within the interacting boson model (IBM) that is based on the nuclear density functional theory is presented. The constrained self-consistent mean-field (SCMF) calculation using a universal energy density functional (EDF) and a pairing interaction provides potential energy surfaces with triaxial quadrupole degrees of freedom for even-even nuclei corresponding to the initial and final states of the $2\nu\beta\beta$ decays of interest. The SCMF energy surface is then mapped onto the bosonic one, and this procedure determines the IBM Hamiltonian for the even-even nuclei. The same SCMF calculation provides the essential ingredients of the interacting boson fermion-fermion model (IBFFM) for the intermediate odd-odd nuclei and the Gamow-Teller and Fermi transition operators. The EDF-based IBM and IBFFM provide a simultaneous description of excitation spectra and electromagnetic transition rates for each nucleus, and single-$\beta$ and $\beta\beta$ decay properties. The calculated $2\nu\beta\beta$-decay nuclear matrix elements are compared with experiment and with those from earlier theoretical calculations.

Charge radii of potassium isotopes in the RMF (BCS)* approach * *This work is partly Supported by the National Natural Science Foundation of China (11735003, 11975041, 11775014, 11961141004), the fundamental Research Funds for the Central Universities; Supported by the National Natural Science Foundation of China (12135004, 11635003, 11961141004, 12047513), and the Reform and Development Project of Beijing Academy of Science

We apply the recently proposed RMF (BCS)* ansatz to study the charge radii of the potassium isotopic chain up to 52K. It is shown that the experimental data can be reproduced rather well, qualitatively similar to the Fayans nuclear density functional theory, but with a slightly better description of the odd–even staggerings (OES). Nonetheless, both methods fail for 50K and to a lesser extent for 48,52K. It is shown that if these nuclei are deformed with a , then one can obtain results consistent with experiments for both charge radii and spin-parities. We argue that beyond-mean-field studies are needed to properly describe the charge radii of these three nuclei, particularly for 50K.

Molecular Dynamics with Constrained Nuclear Electronic Orbital Density Functional Theory: Accurate Vibrational Spectra from Efficient Incorporation of Nuclear Quantum Effects.

Nuclear quantum effects play a crucial role in many chemical and biological systems involving hydrogen atoms yet are difficult to include in practical molecular simulations. In this paper, we combine our recently developed methods of constrained nuclear-electronic orbital density functional theory (cNEO-DFT) and constrained minimized energy surface molecular dynamics (CMES-MD) to create a new method for accurately and efficiently describing nuclear quantum effects in molecular simulations. By use of this new method, dubbed cNEO-MD, the vibrational spectra of a set of small molecules are calculated and compared with those from conventional ab initio molecular dynamics (AIMD) as well as from experiments. With the same formal scaling, cNEO-MD greatly outperforms AIMD in describing the vibrational modes with significant hydrogen motion characters, demonstrating the promise of cNEO-MD for simulating chemical and biological systems with significant nuclear quantum effects.

Bis-(Fluorene)-Embedded Hexaphyrins.

The polyaromatic hydrocarbon containing expanded porphyrins, bis-(fluorene)-embedded hexaphyrins, were synthesized by condensing fluorene-based tripyrrane with pentafluorobenzaldehyde in CH2Cl2 in the presence of 1 equiv of BF3·OEt2 under an inert atmosphere followed by oxidation with DDQ in open air at room temperature. The reaction worked only when 1 equiv of BF3·OEt2 was added to the reaction mixture under concentrated reaction conditions. The bis-(fluorene)-embedded macrocycles were characterized and studied by high-resolution mass spectrometry (HRMS), nuclear magnetic resonance (NMR), absorption, electrochemical, and density functional theory (DFT)/time-dependent (TD)-DFT techniques. In 1H NMR, the hexaphyrins showed a few broad unresolved resonances at room temperature, but the NMR spectra were well-resolved at lower temperatures, indicating that the hexaphyrins were very flexible. The DFT-optimized structures indicated that the two fluorene units at the crossing point of the figure-eight loop makes an angle of ∼79.73° with each other, the fluorene moieties maintained their own planarity, and one of the fluorene moieties was not involved in conjugation with the rest of the macrocycle. The absorption spectra of hexaphyrins showed one intense sharp band in the higher energy region and a broad band in the lower energy region. The electrochemical studies indicated that expanded hexaphyrins are relatively electron-rich and showed three easier oxidations and one reduction. The DFT/TD-DFT studies are in agreement with the experimental observations.

Driving to a Better Understanding of Acyl Glucuronide Transformations Using NMR and Molecular Modeling.

Acyl glucuronide (AG) metabolites of carboxylic acid-containing drugs and products of their transformations have long been implicated in drug-induced liver injury (DILI). To inform on the DILI risk arising from AG reactive intermediates, a comprehensive mechanistic study of enzyme-independent AG rearrangements using nuclear magnetic resonance (NMR) and density functional theory (DFT) was undertaken. NMR spectroscopy was utilized for structure elucidation and kinetics measurements of nine rearrangement and hydrolysis products of 1β-O-acyl glucuronide of ibufenac. To extract rate constants of rearrangement, mutarotation, and hydrolysis from kinetic data, 11 different kinetic models were examined. Model selection and estimated rate constant verification were supported by measurements of H/D kinetic isotope effects. DFT calculations of ground and transition states supported the proposed kinetic mechanisms and helped to explain the unusually fast intramolecular transacylation rates found for some of the intermediates. The findings of the current study reinforce the notion that the short half-life of parent AG and slow hydrolysis rates of AG rearrangement products are the two key factors that can influence the in vivo toxicity of AGs.

Exploring Structural Nuances in Germanium Halide Perovskites Using Solid-State 73Ge and 133Cs NMR Spectroscopy.

Metal halide perovskites remain top candidates for higher-performance photovoltaic devices, but concerns about leading lead-based materials remain. Ge perovskites remain understudied for use in solar cells compared to their Sn-based counterparts. In this work, we undertake a combined 73Ge and 133Cs solid-state Nuclear Magnetic Resonance (NMR) spectroscopy and density functional theory (DFT) study of the bulk CsGeX3 (X = Cl, Br, or I) series. We show how seemingly small structural variations within germanium halide perovskites have major effects on their 73Ge and 133Cs NMR signatures and reveal a near-cubic phase at room temperature for CsGeCl3 with severe local Ge polyhedral distortion. Quantum chemical computations are effective at predicting the structural impact on NMR parameters for 73Ge and 133Cs. This study demonstrates the value of a combined solid-state NMR and DFT approach for investigating promising materials for energy applications, providing information that is out of reach with conventional characterization methods, and adds the challenging 73Ge nucleus to the NMR toolkit.

Toward ab initio charge symmetry breaking in nuclear energy density functionals

We propose a new approach to determine the strength of the charge symmetry breaking (CSB) term in the framework of nuclear density functional theory. It is shown that once ab initio calculations are available including accurate description of isospin symmetry breaking terms in medium and heavy nuclei, the mass difference of mirror nuclei as well as the neutron-skin thickness of doubly-closed-shell nuclei can be used to constrain the strength of the CSB interaction with an uncertainty less than 6%, separately from other isospin symmetry breaking forces. This method opens a new vista of ab initio nuclear energy density functionals.

Universal trend of charge radii of even-even Ca–Zn nuclei

Radii of nuclear charge distributions carry information about the strong and electromagnetic forces acting inside the atomic nucleus. While the global behavior of nuclear charge radii is governed by the bulk properties of nuclear matter, their local trends are affected by quantum motion of proton and neutron nuclear constituents. The measured differential charge radii $\delta\langle r^2_c\rangle$ between neutron numbers $N=28$ and $N=40$ exhibit a universal pattern as a function of $n=N-28$ that is independent of the atomic number. Here we analyze this remarkable behavior in even-even nuclei from calcium to zinc using two state-of-the-art theories based on quantified nuclear interactions: the ab-initio coupled cluster theory and nuclear density functional theory. Both theories reproduce the smooth rise of differential charge radii and their weak dependence on the atomic number. By considering a large set of isotopic chains, we show that this trend can be captured by just two parameters: the slope and curvature of ${\delta\langle r^2_c\rangle(n)}$. We demonstrate that these parameters show appreciable model dependence, and the statistical analysis indicates that they are not correlated with any single model property, i.e., they are impacted by both bulk nuclear properties as well as shell structure.

Fluorocyclopropane-Containing Proline Analogue: Synthesis and Conformation of an Item in the Peptide Chemist's Toolbox.

Over the years, numerous modifications to the structure of proline have been made in order to tune its effects on bioactive compounds. Notably, the introduction of a cyclopropane ring or a fluorine atom has produced interesting results. Herein, we describe the synthesis of a proline containing fluorocyclopropane. This modified amino acid was inserted into a tripeptide, whose conformation was studied by nuclear magnetic resonance and density functional theory calculations.

Sensitive fluorescent determination of indium (III) by a thiourea–quinoline-based chemosensor

A new thiourea–quinoline-based chemosensor ATU (1-(4-acetylphenyl)-3-(quinolin-8-yl)thiourea) was developed for the determination of In3+ using the fluorescence turn-on response. ATU was able to determine In3+ in the presence of Ga3+ and Al3+. The results of a Job’s plot and electrospray ionization–mass spectrometry (ESI–MS) showed that ATU bound to In3+ in a 1:2 stoichiometry ratio. The detection limit for In3+ was 0.64 μM and the binding constant (K) was 5.0 × 1010 M−2, which is the highest value for In3+ chemosensors reported to date. Furthermore, ATU was employed in fluorescent test kits to detect In3+. Moreover, the mechanism of ATU for In3+ determination was evaluated by 1H nuclear magnetic resonance (NMR) titrations and density functional theory (DFT) calculations.

Simultaneous elevation of acid-insoluble lignin and syringyl lignin is the preliminary Cd detoxification strategy in a Cd pollution-safe cultivar (Cd-PSC) of Brassica parachinensis L.

Cadmium (Cd) immobilization in the cell wall is responsible for Cd detoxification in Cd-accumulating cultivars. Lignin is the dominant constituent of the secondary cell wall (SCW), but its role in Cd compartmentalization is poorly understood. The mechanism of Cd compartmentalization by lignin was thus investigated herein. Lignin content and composition, as well as related genes and proteins, were analyzed in the Cd pollution-safe cultivar Brassica parachinensis L. ‘SJ19’. The lignin microstructural regions and Cd affinities were characterized by 2D-heteronuclear single quantum coherence nuclear magnetic resonance (HSQC NMR) and density functional theory (DFT). Lignin combined with 14.2% of the total Cd in SJ19, with a higher Cd distribution in acid-insoluble lignin (AIL). Additionally, the proportion of AIL increased under Cd treatment. The increase in the proportion of the lignin aromatic region syringyl (S) and decrease in the guaiacyl (G) proportion were in accordance with the significant up-regulation of peroxidase P7 and down-regulation of caffeoyl-CoA O-methyltransferase At1g67980 under Cd stress. Moreover, the Cd affinity associating with the lignin aromatic region ranked as S > G> H (p-hydroxyphenyl). Therefore, rather than lignin biosynthesis, the simultaneous elevation of AIL and S lignin was recognized as the preliminary strategy for lignin compartmentalization of Cd in SCW for the first time herein. This is beneficial for Cd detoxification in the Cd pollution-safe cultivar of B. parachinensis.

Photocatalytic Selective Oxidation of HMF Coupled with H2 Evolution on Flexible Ultrathin g-C3N4 Nanosheets with Enhanced N–H Interaction

Solar-driven catalytic oxidation of 5-hydroxymethylfurfural (HMF) into 2,5-diformylfuran (DFF) coupled with H2 evolution has been considered a promising approach. The exploration of an active and stable photocatalyst still remains challenging work. Herein, we found that the flexible ultrathin graphitic carbon nitride (UCNT) could be an ideal candidate. The UCNT exhibits photocatalytic performance in selective oxidation of HMF into DFF coupled with H2 evolution with activities of 95.0 and 92.0 μmol g–1 h–1 under visible light irradiation. Importantly, the UCNT also demonstrates high DFF selectivity (95%) and good cycling stability. The activity may be ascribed to the strong specific interaction between HMF and UCNT. Solid-state nuclear magnetic resonance (NMR) and density functional theory (DFT) results reveal that the twisted structure of HMF molecules could form a strong interaction between HMF and UCNT, reducing the dehydrogenation energy barrier for HMF oxidation. In addition, mechanistic studies reveal that •C6H4O3 is the key radical intermediate during the HMF oxidation process by a in situ electron spin resonance (ESR) trapping test. Our work clarifies the interaction of complex biomass molecules on the flexible catalyst surface and provides views on the further development of heterogeneous catalytic biomass conversion.