Study of multi-quasiparticle excited states in Ce-139

High-spin states in Ce-139 have been populated using the Te-130(C-12, 3n) reaction at beam energy of 50MeV. The level scheme of Ce-139 has been revised and extended greatly up to E=5765.0keV. The level structure of Ce-139 shows typical characteristics of spherical nucleus, and the high-spin states were formed by the excitations of valence nucleons. Energies of the yrast and near yrast high-spin states in Ce-139 have been calculated by the empirical shell model, and the multi-quasiparticle nature of high-spin excited states has been discussed.

Study of quasiparticles bands in odd-odd Au-188

High-spin level structure of Au-188 has been studied via the Yb-173(F-19, 4n gamma) reaction using techniques of in-beam gamma-ray spectroscopy. Based on the experimental results, the level scheme of 188Au has been revised significantly. The previously reported positive parity levels have been modified and a new 20(+) level was proposed to feed the 18(+) states via two low-energy transitions. The existence of the 20(+) and the level structures above it are similar to those in the neighboring odd-odd Au-190,Au-192, therefore, the pi h(11/12)(-1)circle times-vi(13/2)(-2)h(9/2)(-1) configuration was assigned to the 20(+) state.

143Pm高自旋态和重丰中子新核素的合成及衰变性质研究

本论文从内容上可以分为两大部分：第一部分：对近球形核~(143)Pm高自旋态进行的在束γ研究。这一部分是本文的重点。利用能量为82和90 MeV的~(19)F束流，通过融合蒸发反应~(128)Te (~(19)F,4nγ) ~(143)Pm布局~(143)Pm的高自旋态。利用联合在束装置(JIBGE)的10套带BGO反康的HPGe探测器进行了标准在束γ谱学测量，包括γ射线的激发函数、γ单谱、γ-γ-t符合谱以及DCO测量。在已有工作的基础上，建立了~(143)Pm激发能高达10.5 MeV，自旋约为(61/2)h的高自旋态能级结构。观测到了28条新的跃迁能级和48条新的γ射线。对两个已知的同质异能态寿命进行了提取，并在8 MeV激发能附近进行了高自旋态同质异能态的搜索。以~(142)Nd，~(144)Sm为核实，用零级弱耦合模型对~(143)Pm的晕态能级结构进行了定量的解释。计算表明，直到激发能Ex = 6.77 MeV，自旋宇称J~π = (37/2~+)的晕态能级都可以用弱耦合模型进行很好的解释。但是，对于更高激发能的能级，组态情况要复杂的多，有出现N = 82中子闭壳打破的可能。同时，利用大基壳模型OXBASH程序对其能级结构进行了计算和讨论，其结果支持弱耦合模型的假设。第二部分：利用中能重离子的多核子转移反应，(~(186)W-2p + 2n)，(~(238)U-2p + 2n)对丰中子核~(186)Hf和~(238)Th进行了合成和鉴别。测量它们的半衰期分别为(2.6 ± 1.2) min和 (9.4 ± 2.0) min，与用质子一中子准粒子随机相近似方法的预言值是相符的。同时，对β延发裂变先驱核~(230)Ac进行了实验研究。观测到了它的两个裂变事件，得到~(230)Acβ延发裂变几率为(1.19 ± 0.85) * 10~(-8)。从而使~(230)Ac成为世界上第一种被确认了的基态β延发裂变先驱核。

Ferrimagnetic and semiconducting CaCu3Fe2Sb2O12 by first principles

CaCu3Fe2Sb2O12 is mechanically stable, thermodynamically stable at pressures above 18 GPa. Both GGA and GGA + U methods predict that it is a ferrimagnetic semiconductor with Fe3+ in high spin state (S = 5/2). The coupling of Fe-Cu is antiferromagnetic, while that of Cu-Cu is ferromagnetic. The calculated total spin moment is 6.17 mu(B).

Structures and vibrational spectra of C-2 and LaC2+ clusters

C-2 and LaC2+ were studied using Hartree-Fock(HF), B3LYP (Becke 3-paremeter-Lee-Yang-Parr) density functional method, second-order Moller-Plesset perturbation (MP2) and coupled cluster singles and doubles with non-iterative triples(CCSD(T)) methods. The basis set employed was LANL1DZ. Geometries, vibrational frequencies and other quantities were reported. The results showed that for C-2, all the methods performed well for low spin state (singlet), while only HF and B3LYP remained so for high spin state (triplet). For LaC2+, four isomers were presented and fully optimized. The results suggested that linear isomers with C-infinity v and D-infinity h symmetries were predicted to be saddle points on the energy surface for all the methods, while for isomers with C-2 upsilon and C-s symmetries, they were local minima except C-2 upsilon at B3LYP level, and were isoenergetic at HF, MP2 and CCSD(T) levels, near isoenergetic at B3LYP level. From the differences between HOMO and LUMO, it is also known that the isomers with C-2 upsilon and C-s symmetries offer the largest values and therefore correspond to the most stable structure. For La-C bond lengths, B3LYP gives the shortest, the order is B3LYP

MAGNETIC-PROPERTIES OF LANTHANUM MANGANITE AND VALENCE EQUILIBRIA OF MANGANESE

The paramagnetic susceptibility of lanthanum manganite has been measured over a wide temperature range (100-1073 K). On the basis of the thermodynamic equilibria between the various manganese ions with different valence and spin states and the magnetic interactions between the various manganese ions, a semiempirical formula has been proposed to calculate the paramagnetic susceptibilities of lanthanum manganite at different temperatures. The results indicate that most of the discrepancies between the calculated and experimental reciprocal susceptibilities of lanthanum manganite are less than 10% and that the relative contents of the various manganese ions in lanthanum manganite vary with temperature. The relative content of the trivalent manganese ion with a high spin state is dominant over the whole temperature range, while be relative content of the tetravalent manganese ion with a high spin state decreases monotonously with increasing temperature. At 300 K the calculated relative content of the tetravalent manganese ion in lanthanum manganite is about 34%, which is in good agreement with the experimental result (30%). There are some divalent manganese ions present in lanthanum manganite from low temperature to high temperature. The ratio of the relative contents of the tetravalent and divalent manganese ions in the compound varies with temperature. Above 750 K the relative content of the tetravalent manganese ion is less than that of the divalent manganese ion. The variation in the electrical resistivity of lanthanum manganite with temperature has also been interpreted reasonably.

Synthesis and spectral investigations of Mn(II) complexes of pentadentate bis(thiosemicarbazones)

Five Mn(II) complexes of bis(thiosemicarbazones) which are represented as [Mn(H2Ac4Ph)Cl2] (1), [Mn(Ac4Ph)H2O] (2), [Mn(H2Ac4Cy)Cl2]·H2O (3), [Mn(H2Ac4Et)Cl2]·3H2O (4) and [Mn(H2Ac4Et)(OAc)2]·3H2O (5) have been synthesized and characterized by elemental analyses, electronic, infrared and EPR spectral techniques. In all the complexes except [Mn(Ac4Ph)H2O], the ligands act as pentadentate neutral molecules and coordinate to Mn(II) ion through two thione sulfur atoms, two azomethine nitrogens and the pyridine nitrogen, suggesting a heptacoordination. While in compound [Mn(Ac4Ph)H2O], the dianionic ligand is coordinated to the metal suggesting six coordination in this case. Magnetic studies indicate the high spin state of Mn(II). Conductivity measurements reveal their non-electrolyte nature. EPR studies indicate five g values for [Mn(Ac4Ph)H2O] showing zero field splitting.

A Donor-Acceptor Tetrathiafulvalene Ligand Complexed to Iron(II): Synthesis, Electrochemistry, and Spectroscopy of Fe(phen)(2)(TTF-dppz)(PF6)(2)

The synthesis and photophysical properties of the complex Fe(phen)(2)(TTF-dppz)(2+) (TTF-dppz = 4',5'-bis-(propylthio)tetrathiafulvenylidipyrido3,2-a:2',3'-c-phenazine, phen = 1,10-phenanthroline) are described. In this complex, excitation into the metal ligand charge transfer bands results in the population of a high-spin state of iron(II), with a decay lifetime of approximately 1.5 ns, in dichloromethane, at room temperature. An intraligand charge transfer state can also be obtained and has a lifetime of 38 ps. A mechanism for the different states reached is proposed based on transient absorption spectroscopy.

Remote Effects Modulating the Spin Equilibrium of the Resting State of Cytochrome P450cam –An Investigation Using Active Site Analogues

The crystal structure of the resting state of cytochrome P450cam (CYP101), a heme thiolate protein, shows a cluster of six water molecules in the substrate binding pocket, one of which is coordinating to iron(III) as sixth ligand. The resting state is low-spin and changes to high-spin when substrate camphor binds and H2O is removed. In contrast to the protein, previously synthesised enzyme models such as H2O[BOND]FeIII(porph)(ArS−) were shown to be purely high-spin. Iron(S−)porphyrins with different distal sites mimicking proposed remote effects have been prepared and studied by cw-EPR. The results indicate that the low-spin of the resting state of P450cam is due to the fact that the water molecule coordinating to iron has an OH−-like character because of hydrogen bonding and polarisation of the water cluster, respectively.

Iron(II) spin transition complexes with dendritic ligands, Part I

The ligands G1- and G2-oligo (benzyl ether) (PBE) dendrons and their iron(II) complexes [Fe(Gn-PBE)3]A2·xH2O (with n = 1, 2 and A = triflate, tosylate) were prepared. The magnetic properties of the complexes were investigated by a SQUID magnetometer. All complexes exhibit gradual spin transition below room temperature. At very low temperatures the magnetic behaviour reflects zero-field splitting (ZFS) effects. 57Fe-Mössbauer spectroscopy was performed to distinguish between ZFS of high spin species and spin state conversion into the low spin state. Further characterisation was carried out by thermogravimetric analysis (TGA) and FT-IR spectroscopy. Structural features have been determined by powder XRD measurements.

Studies of electronic structure by x-ray Raman and emission spectroscopy: applications to MgB2 superconductors and high pressure physics

X-ray Raman scattering and x-ray emission spectroscopies were used to study the electronic properties and phase transitions in several condensed matter systems. The experimental work, carried out at the European Synchrotron Radiation Facility, was complemented by theoretical calculations of the x-ray spectra and of the electronic structure. The electronic structure of MgB2 at the Fermi level is dominated by the boron σ and π bands. The high density of states provided by these bands is the key feature of the electronic structure contributing to the high critical temperature of superconductivity in MgB2. The electronic structure of MgB2 can be modified by atomic substitutions, which introduce extra electrons or holes into the bands. X ray Raman scattering was used to probe the interesting σ and π band hole states in pure and aluminum substituted MgB2. A method for determining the final state density of electron states from experimental x-ray Raman scattering spectra was examined and applied to the experimental data on both pure MgB2 and on Mg(0.83)Al(0.17)B2. The extracted final state density of electron states for the pure and aluminum substituted samples revealed clear substitution induced changes in the σ and π bands. The experimental work was supported by theoretical calculations of the electronic structure and x-ray Raman spectra. X-ray emission at the metal Kβ line was applied to the studies of pressure and temperature induced spin state transitions in transition metal oxides. The experimental studies were complemented by cluster multiplet calculations of the electronic structure and emission spectra. In LaCoO3 evidence for the appearance of an intermediate spin state was found and the presence of a pressure induced spin transition was confirmed. Pressure induced changes in the electronic structure of transition metal monoxides were studied experimentally and were analyzed using the cluster multiplet approach. The effects of hybridization, bandwidth and crystal field splitting in stabilizing the high pressure spin state were discussed. Emission spectroscopy at the Kβ line was also applied to FeCO3 and a pressure induced iron spin state transition was discovered.

Relative entropy in higher spin holography

We examine relative entropy in the context of the higher spin/CFT duality. We consider 3D bulk configurations in higher spin gravity which are dual to the vacuum and a high temperature state of a CFT with W-algebra symmetries in the presence of a chemical potential for a higher spin current. The relative entropy between these states is then evaluated using the Wilson line functional for holographic entanglement entropy. In the limit of small entangling intervals, the relative entropy should vanish for a generic quantum system. We confirm this behavior by showing that the difference in the expectation values of the modular Hamiltonian between the states matches with the difference in the entanglement entropy in the short-distance regime. Additionally, we compute the relative entropy of states corresponding to smooth solutions in the SL(2, Z) family with respect to the vacuum.

I. Electron spin relaxation studies of manganese(II) complexes in acetonitrile. II. Nuclear spin relaxation studies of bromine in tetrabromomanganese(II) in acetonitrile

Magnetic resonance techniques have given us a powerful means for investigating dynamical processes in gases, liquids and solids. Dynamical effects manifest themselves in both resonance line shifts and linewidths, and, accordingly, require detailed analyses to extract desired information. The success of a magnetic resonance experiment depends critically on relaxation mechanisms to maintain thermal equilibrium between spin states. Consequently, there must be an interaction between the excited spin states and their immediate molecular environment which promote changes in spin orientation while excess magnetic energy is coupled into other degrees of freedom by non-radiative processes. This is well known as spin-lattice relaxation. Certain dynamical processes cause fluctuations in the spin state energy levels leading to spin-spin relaxation and, here again, the environment at the molecular level plays a significant role in the magnitude of interaction. Relatively few electron spin relaxation studies of solutions have been conducted and the present work is addressed toward the extension of our knowledge in this area and the retrieval of dynamical information from line shape analyses on a time scale comparable to diffusion controlled phenomena.

Specifically, the electron spin relaxation of three Mn⁺²3d⁵ complexes, Mn(CH₃CN)₆⁺², MnCl₄^-2 in acetonitrile has been studied in considerable detail. The effective spin Hamiltonian constants were carefully evaluated under a wide range of experimental conditions. Resonance widths of these Mn⁺² complexes were studied in the presence of various excess ligand ions and as a function of concentration, viscosity, temperature and frequency (X-band, ~9.5 Ԍ Hz and K-band, ~35 Ԍ Hz).

A number of interesting conclusions were drawn from these studies. For the Et₄NCl-₄^-2 system several relaxation mechanisms leading to resonance broadening were observed. One source appears to arise through spin-orbit interactions caused by modulation of the ligand field resulting from transient distortions of the complex imparted by solvent fluctuations in the immediate surroundings of the paramagnetic ion. An additional spin relaxation was assigned to the formation of ion pairs [Et₄N⁺…MnCl₄^-2] and it was possible to estimate the dissociation constant for this specie in acetonitrile.

The Bu₄NBr-MnBr₄^-2 study was considerably more interesting. As in the former case, solvent fluctuations and ion-pairing of the paramagnetic complex [Bu₄N⁺…MnBr₄^-2] provide significant relaxation for the electronic spin system. Most interesting, without doubt, is the onset of a new relaxation mechanism leading to resonance broadening which is best interpreted as chemical exchange. Thus, assuming that resonance widths were simply governed by electron spin state lifetimes, we were able to extract dynamical information from an interaction in which the initial and final states are the same

MnBr₄^-2 + Br^- = MnBr₄^-2 + Br^-.

The bimolecular rate constants were obtained at six different temperatures and their magnitudes suggested that the exchange is probably diffusion controlled with essentially a zero energy of activation. The most important source of spin relaxation in this system stems directly from dipolar interactions between the manganese 3d⁵ electrons. Moreover, the dipolar broadening is strongly frequency dependent indicating a deviation between the transverse and longitudinal relaxation times. We are led to the conclusion that the 3d⁵ spin states of ion-paired MnBr₄^-2 are significantly correlated so that dynamical processes are also entering the picture. It was possible to estimate the correlation time, ^Td, characterizing this dynamical process.

In Part II we study nuclear magnetic relaxation of bromine ions in the MnBr4-2-Bu4NBr-acetonitrile system. Essentially we monitor the 79Br and 81Br linewidths in response to the [MnBr4-2]/[Br-] ratio with the express purpose of supporting our contention that exchange is occurring between "free" bromine ions in the solvent and bromine in the first coordination sphere of the paramagnetic anion. The complexity of the system elicited a two-part study: (1) the linewidth behavior of Bu4NBr in anhydrous CH3CN in the absence of MnBr4-2 and (2) in the presence of MnBr4-2. It was concluded in study (1) that dynamical association, Bu4NBr k1= Bu4N+ + Br-, was modulating field-gradient interactions at frequencies high enough to provide an estimation of the unimolecular rate constant, k1. A comparison of the two isotopic bromine linewidth-mole fraction results led to the conclusion that quadrupole interactions provided the dominant relaxation mechanism. In study (2) the "residual" bromine linewidths for both 79Br and 81Br are clearly controlled by quadrupole interactions which appear to be modulated by very rapid dynamical processes other than molecular reorientation. We conclude that the "residual" linewidth has its origin in chemical exchange and that bromine nuclei exchange rapidly between a "free" solvated ion and the paramagnetic complex, MnBr4-2.

Competition in rotation-alignment between high-j neutrons and protons in transfermium nuclei

The study of rotation-alignment of quasiparticles probes sensitively the properties of high-j intruder orbits. The distribution of very-high-j orbits, which are consequences of the fundamental spin-orbit interaction, links with the important question of single-particle levels in superheavy nuclei. With the deformed single-particle states generated by the standard Nilsson potential, we perform Projected Shell Model calculations for transfermium nuclei where detailed spectroscopy experiments are currently possible. Specifically, we study the systematical behavior of rotation-alignment and associated band-crossing phenomenon in Cf, Fm, and No isotopes. Neutrons and protons from the high-j orbits are found to compete strongly in rotation-alignment, which gives rise to testable effects. Observation of these effects will provide direct information on the single-particle states in the heaviest nuclear mass region.