Nuclear Density Functional Theory Research Articles

ISOSPIN MIXING IN THE VICINITY OF THE N = Z LINE

We present the isospin- and angular-momentum-projected nuclear density functional theory (DFT) and its applications to the isospin-breaking corrections to the superallowed β-decay rates in the vicinity of the N = Z line. A preliminary value obtained for the Cabibbo–Kobayashi–Maskawa matrix element, |Vud| = 0.97463(24), agrees well with the recent estimate by Towner and Hardy [Phys. Rev.C77, 025501 (2008)]. We also discuss new opportunities to study the symmetry energy by using the isospin-projected DFT.

Seco-Limonoids and Quinoline Alkaloids from Raputia heptaphylla and Their Antileishmanial Activity

A novel seco-limonoid, rel-(1S,5R,9S,7R,8S,9R,10S,11R,13S,14R,15R,17R)-11,19-dihydroxy-7-acetoxy-7-deoxoichangin (raputiolide) (1), and two novel quinolone alkaloids N-methyl-2-phenoxyquinolin-4(1H)-one (heptaphyllone A) (2) and 6-methylbenzofuro[2,3-b]quinolin-4(1H)-one (heptaphyllone B) (3), along with the known seco-limonoid ichangin (4), were isolated from Raputia heptaphylla PITTIER (Rutaceae) stem bark. Five known alkaloids, N-methyl-8-methoxyflindersine (5), skimmianine (6), kokusaginine (7), dictamnine (8) and flindersiamine (9), were also isolated from R. heptaphylla leaves. Their structures were established on the basis of full spectroscopic data interpretation supported by data from the pertinent literature. seco-Limonoid 1 configuration was determined by enhanced nuclear Overhauser effect spectroscopy (NOESY) experiments and density functional theory (DFT) molecular modeling. The antileishmanial effect of the isolated compounds was evaluated on Leishmania Viannia panamensis (promastigotes and amastigotes). Whereas alkaloids 2-3, 6-8 and limonoid 4 exhibited no significant parasitocide activity against internalized L. (V.) panamensis amastigotes, limonoid 1 and alkaloid 5 had leishmanicidal activity on intracellular amastigotes (EC₅₀: 8.7 µg/ml) and promastigotes (EC(50): 14.3 µg/ml), respectively.

Towards understanding the poor thermal stability of V 5+ electrolyte solution in Vanadium Redox Flow Batteries

The V 5+ electrolyte solution from Vanadium Redox Flow Batteries was studied by variable temperature 17O and 51V Nuclear Magnetic Resonance (NMR) spectroscopy and density functional theory (DFT) based computational modeling. It was found that the V 5+ species exist as hydrated penta co-ordinated vanadate ion, i.e. [VO 2(H 2O) 3] 1+. This hydrated structure is not stable at elevated temperature and change into neutral H 3VO 4 molecule via a deprotonation process and subsequently leading to the observed V 2O 5 precipitation in V 5+ electrolyte solutions.

Spin and spin-isospin instabilities in asymmetric nuclear matter at zero and finite temperatures using Skyrme functionals

Self-consistent mean field methods based on phenomenological Skyrme effective interactions are known to exhibit spurious spin and spin-isospin instabilities both at zero and finite temperatures when applied to homogeneous nuclear matter at the densities encountered in neutron stars and in supernova cores. The origin of these instabilities is revisited in the framework of the nuclear energy density functional theory and a simple prescription is proposed to remove them. The stability of several Skyrme parametrizations is reexamined.

Structure and Dynamics of [3.3]Paracyclophane As Studied by Nuclear Magnetic Resonance and Density Functional Theory Calculations

Strained cyclophanes with small (-CH(2)-)(n) bridges connecting two benzene rings are interesting objects of basic research, mostly because of the nonplanarity of the rings and of interference of π-electrons of the latter. For title [3.3]paracyclophane, in solutions occurring in two interconverting cis and trans conformers, the published nuclear magnetic resonance (NMR) data are incomplete and involve its partially deuterated isotopomers. In this paper, variable-temperature NMR studies of its perprotio isotopomer combined with DFT quantum chemical calculations provide a complete characterization of the solution structure, NMR parameters, and interconversion of the cis and trans isomers of the title compound. Using advanced methods of spectral analysis, total quantitative interpretation of its proton NMR spectra in both the static and dynamic regimes is conducted. In particular, not only the geminal but also all of the vicinal J(HH) values for the bridge protons are determined, and for the first time, complete Arrhenius data for the interconversion process are reported. The experimental proton and carbon chemical shifts and the (n)J(HH), (1)J(CH), and (1)J(CC) coupling constants are satisfactorily reproduced theoretically by the values obtained from the density functional theory calculations.

Augmented Lagrangian method for constrained nuclear density functional theory

The augmented Lagrangiam method (ALM), widely used in quantum chemistry constrained optimization problems, is applied in the context of the nuclear Density Functional Theory (DFT) in the self-consistent constrained Skyrme Hartree-Fock-Bogoliubov (CHFB) variant. The ALM allows precise calculations of multidimensional energy surfaces in the space of collective coordinates that are needed to, e.g., determine fission pathways and saddle points; it improves accuracy of computed derivatives with respect to collective variables that are used to determine collective inertia; and is well adapted to supercomputer applications.

Natural units for nuclear energy density functional theory

Naive dimensional analysis based on chiral effective theory, when adapted to nuclear energy density functionals, prescribes natural units and a hierarchy of contributions that could be used to constrain fits of generalized functionals. By applying these units, a large sample of Skyrme parametrizations is examined for naturalness, which is signaled by dimensionless coupling constants of order one. The bulk of the parameters are found to be natural, with an underlying scale consistent with other determinations. Significant deviations from unity are associated with deficiencies in the corresponding terms of particular functionals or with an incomplete optimization procedure.

Isospin-symmetry restoration within the nuclear density functional theory: Formalism and applications

Isospin symmetry of atomic nuclei is explicitly broken by the charge-dependent interactions, primarily the Coulomb force. Within the nuclear density functional theory, isospin is also broken spontaneously. We propose a projection scheme rooted in a Hartree-Fock theory that allows the consistent treatment of isospin breaking in both ground and exited nuclear states. We demonstrate that this scheme is free from spurious divergences plaguing particle-number and angular-momentum restoration approaches. Applications of the new technique include excited high-spin states in medium-mass $N=Z$ nuclei, such as superdeformed bands and many-particle--many-hole terminating states. Owing to the large spin polarization and/or high seniority of these states, pairing correlations have been ignored.

SPATIAL SYMMETRIES OF THE LOCAL DENSITIES

Spatial symmetries of the densities appearing in the nuclear Density Functional Theory are discussed. General forms of the local densities are derived by using methods of construction of isotropic tensor fields. The spherical and axial cases are considered.

Open problems in nuclear density functional theory

This paper describes five questions of some interest for the density functional theory in nuclear physics. These are, respectively, (i) the need for concave functionals, (ii) the nature of the Kohn–Sham potential for the radial density theory, (iii) a proper implementation of a density functional for an ‘intrinsic’ rotational density, (iv) the possible existence of a potential driving the square root of the density and (v) the existence of many models where a density functional can be explicitly constructed.

One-quasiparticle states in the nuclear energy density functional theory

We study one-quasiproton excitations in the rare-earth region in the framework of the nuclear density functional theory in the Skyrme-Hartree-Fock-Bogoliubov variant. The blocking prescription is implemented exactly, with the time-odd mean field fully taken into account. The equal filling approximation is compared with the exact blocking procedure. We show that both procedures are strictly equivalent when the time-odd channel is neglected and discuss how nuclear alignment properties affect the time-odd fields. The impact of time-odd fields on calculated one-quasiproton band-head energies is found to be rather small, of the order of $100--200$ keV; hence, the equal filling approximation is sufficiently precise for most practical applications. The triaxial polarization of the core induced by the odd particle is studied. We also briefly discuss the occurrence of finite-size spin instabilities that are present in calculations for odd-mass nuclei when certain Skyrme functionals are employed.

Self-consistent symmetries in the proton-neutron Hartree-Fock-Bogoliubov approach

Symmetry properties of densities and mean fields appearing in the nuclear Density Functional Theory with pairing are studied. We consider energy functionals that depend only on local densities and their derivatives. The most important self-consistent symmetries are discussed: spherical, axial, space-inversion, and mirror symmetries. In each case, the consequences of breaking or conserving the time-reversal and/or proton-neutron symmetries are discussed and summarized in a tabulated form, useful in practical applications.

Direct Evidence for Nitrogen Ligation to the High Stability Semiquinone Intermediate in Escherichia coli Nitrate Reductase A

The membrane-bound heterotrimeric nitrate reductase A (NarGHI) catalyzes the oxidation of quinols in the cytoplasmic membrane of Escherichia coli and reduces nitrate to nitrite in the cytoplasm. The enzyme strongly stabilizes a menasemiquinone intermediate at a quinol oxidation site (Q(D)) located in the vicinity of the distal heme b(D). Here molecular details of the interaction between the semiquinone radical and the protein environment have been provided using advanced multifrequency pulsed EPR methods. (14)N and (15)N ESEEM and HYSCORE measurements carried out at X-band ( approximately 9.7 GHz) on the wild-type enzyme or the enzyme uniformly labeled with (15)N nuclei reveal an interaction between the semiquinone and a single nitrogen nucleus. The isotropic hyperfine coupling constant A(iso)((14)N) approximately 0.8 MHz shows that it occurs via an H-bond to one of the quinone carbonyl group. Using (14)N ESEEM and HYSCORE spectroscopies at a lower frequency (S-band, approximately 3.4 GHz), the (14)N nuclear quadrupolar parameters of the interacting nitrogen nucleus (kappa = 0.49, eta = 0.50) were determined and correspond to those of a histidine N(delta), assigned to the heme b(D) ligand His-66 residue. Moreover S-band (15)N ESEEM spectra enabled us to directly measure the anisotropic part of the nitrogen hyperfine interaction (T((15)N) = 0.16 MHz). A distance of approximately 2.2 Abetween the carbonyl oxygen and the nitrogen could then be calculated. Mechanistic implications of these results are discussed in the context of the peculiar properties of the menasemiquinone intermediate stabilized at the Q(D) site of NarGHI.

Structural Study of Selected Polyhalogenated Benzimidazoles (Protein Kinase CK2 Inhibitors) by Nuclear Quadrupole Double Resonance, X-ray, and Density Functional Theory

Protein kinase CK2 inhibitors, polyhalogenated benzimidazoles, have been studied experimentally in solid state by NMR-NQR double resonance and X-ray and theoretically by the density functional theory (DFT). Six resonance frequencies on (14)N have been detected and assigned to particular nitrogen sites in each polyhalogenated benzimidazole molecule. The effects of prototropic annular tautomerism and polymorphism related to stable cluster formation due to intermolecular hydrogen bonding interactions on the (14)N NQR parameters have been analyzed within the DFT and AIM (atoms in molecules) formalism. The studies suggest that all polyhalogenobenzimidazoles are isostructural and can exhibit polymorphism and that (14)N NQR is very sensitive to hydrogen bondings but less sensitive to the specific arrangement of the hydrogen bonded molecules. NQDR and DFT results suggest the presence of the prototropic annular tautomerism 50:50, which is in a good agreement with the X-ray and (1)H NMR data.

Selective Chelation of Cd(II) and Pb(II) versus Ca(II) and Zn(II) by Using Octadentate Ligands Containing Pyridinecarboxylate and Pyridyl Pendants

Herein we report the coordination properties toward Cd(II), Pb(II), Ca(II), and Zn(II) of a new octadentate ligand (py-H(2)bcpe) based on a ethane-1,2-diamine unit containing two picolinate and two pyridyl pendants, which is structurally derived from the previous reported ligand bcpe. Potentiometric studies have been carried out to determine the protonation constants of the ligand and the stability constants of the complexes with these cations. The introduction of the pyridyl pendants in bcpe provokes a very important increase of the logK(ML) values obtained for the Pb(II) and Cd(II) complexes, while this effect is less important in the case of the Zn(II) analogue. As a result, py-bcpe shows a certain selectivity for Cd(II) and Pb(II) over Zn(II) while keeping good Pb(II)/Ca(II) and Cd(II)/Ca(II) selectivities, and the new receptor py-bcpe can be considered as a new structural framework for the design of novel Cd(II) and Pb(II) extracting agents. Likewise, the stabilities of the Cd(II) and Pb(II) complexes are higher than those of the corresponding EDTA analogues. The X-ray crystal structure of [Zn(py-bcpe)] shows hexadentate binding of the ligand to the metal ion, the coordination polyhedron being best described as a severely distorted octahedron. However, the X-ray crystal structure of the Pb(II) analogue shows octadentate binding of the ligand to the metal ion. A detailed investigation of the structure in aqueous solution of the complexes by using nuclear magnetic resonance (NMR) techniques and density functional theory (DFT) calculations (B3LYP) shows that while in the Zn(II) complex the metal ion is six-coordinated, in the Pb(II) and Ca(II) analogues the metal ions are eight-coordinated. For the Cd(II) complex, our results suggest that in solution the complex exists as a mixture of seven- and eight-coordinated species. DFT calculations performed both in the gas phase and in aqueous solution have been also used to investigate the role of the Pb(II) lone pair in the structure of the [Pb(py-bcpe)] complex.

Microscopic description of complex nuclear decay: Multimodal fission

Our understanding of nuclear fission, a fundamental nuclear decay, is still incomplete due to the complexity of the process. In this paper, we describe a study of spontaneous fission using the symmetry-unrestricted nuclear density functional theory. Our results show that the observed bimodal fission can be explained in terms of pathways in multidimensional collective space corresponding to different geometries of fission products. We also predict a new phenomenon of trimodal spontaneous fission for some rutherfordium, seaborgium, and hassium isotopes.

Isospin Mixing in Nuclei within the Nuclear Density Functional Theory

We present the self-consistent, nonperturbative analysis of isospin mixing using the nuclear density functional approach and the rediagonalization of the Coulomb interaction in the good-isospin basis. The unphysical isospin violation on the mean-field level, caused by the neutron excess, is eliminated by the proposed method. We find a significant dependence of the magnitude of isospin breaking on the parametrization of the nuclear interaction. A rough correlation has been found between the isospin-mixing parameter and the difference of proton and neutron rms radii.

Fission Barriers of Compound Superheavy Nuclei

The dependence of fission barriers on the excitation energy of the compound nucleus impacts the survival probability of superheavy nuclei synthesized in heavy-ion fusion reactions. In this work, we investigate the isentropic fission barriers by means of the self-consistent nuclear density functional theory. The relationship between isothermal and isentropic descriptions is demonstrated. Calculations have been carried out for 264Fm, 272Ds, ;{278}112, ;{292}114, and ;{312}124. For nuclei around ;{278}112 produced in "cold-fusion" reactions, we predict a more rapid decrease of fission barriers with excitation energy as compared to the nuclei around ;{292}114 synthesized in "hot-fusion" experiments. This is explained in terms of the difference between the ground-state and saddle-point temperatures. The effect of the particle gas is found to be negligible in the range of temperatures studied.

LARGE-SCALE MASS TABLE CALCULATIONS

Systematic self-consistent nuclear mass calculations, based on the nuclear density functional theory, represent a rich scientific agenda that is closely aligned with the main research directions in modern nuclear structure and astrophysics, especially in the context of the radioactive nuclear beam physics. The status of large-scale mass calculations carried out under the UNEDF project and the development of the mass-table visualization software are briefly discussed.

ADIABATIC MASS PARAMETERS FOR SPONTANEUS FISSION

The collective mass tensor derived from the adiabatic time-dependent Hartree-Fock-Bogoliubov theory, perturbative cranking approximation, and the Gaussian overlap approximation to the generator coordinate method is discussed. Illustrative calculations are carried out for 252 Fm using the nuclear density functional theory with Skyrme interaction SkM* and seniority pairing.