Medium-spin states in Ge-70 and the role of the g(9/2) orbital

Medium-spin states of Ge-70 have been studied via the Ni-60(C-12,2p gamma)Ge-70 reaction at 45 MeV. The ground-state band and the second 0(+) band have been extended to the 12(+) and 8(+) states, respectively. Two negative-parity bands, one of which has a coupled structure and the other has a decoupled structure, have been observed additionally. Although the latter decoupled structure was known up to the (21(-)) state from a previous experiment, the part of the level scheme up to the 15(-) state has been largely modified by the present experiment. Backbendings observed in the positive- and negative-parity yrast bands have been compared with those of the neighboring even Ge isotopes. The experimental level structure has been compared with the shell-model calculations in the model space (2p(3/2), 1f(5/2), 2(p1/2), 1g(9/2)) employing two kinds of effective interactions, one of which is an extended P + QQ interaction with monopole interactions and the other is developed from a renormalized G matrix. Microscopic structures of the observed bands have been discussed with the help of the shell-model calculations.

Determination of arsenic species by capillary zone electrophoresis with large-volume field-amplified stacking injection

Determination of arsenic species by large-volume field amplified stacking injection-capillary zone electrophoresis (LV-FASI-CZE) is reported in this paper. Whole column injection was employed. The optimum buffer pH for the separation of weak acids was discussed. It was found that the optimum buffer to analyze the stacked arsenate (As(V)), monomethylarsonate (MMA), and dimethylarsinate (DMA) was 25 mm phosphate at pH 6.5. However, the optimum buffer to analyze the concentrated arsenite (As(III)) was 20 mm phosphate - 10 mm borate at pH 9.28. The limits of detection of the method developed were 0.026 mg/L for As(III), 0.023 mg/L for As(V), 0.043 mg/L for MMA, and 0.018 mg/L for DMA. An enrichment factor of 34-100 for several arsenic species was obtained. In the end, this method was applied to determine the arsenic concentration in the environmental reference materials to show the usefulness of the method developed.

Magnetic structure and orbital ordering in tetragonal and monoclinic KCrF3 from first-principles calculations

KCrF3 has been systematically investigated by using the full-potential linearized augmented plane wave plus local orbital method within the generalized gradient approximation and the local spin density approximation plus the on-site Coulomb repulsion approach. The total energies for ferromagnetic and three different antiferromagnetic configurations are calculated in the high-temperature tetragonal and low-temperature monoclinic phases, respectively.

Spontaneous volume transition of polyampholyte nanocomposite hydrogels based on pure electrostatic interaction

A circular system is employed in this paper to investigate the swelling behaviors of polyampholyte hydrogels; this circular system can effectively eliminate the disturbance of various factors and keep the surrounding environment constant. It is found that there exists a spontaneous volume transition to the collapsed state of polyampholyte hydrogels, which is attributed to the overshooting effect, and the transition can occur repeatedly under certain conditions. C-13 NMR is employed to investigate the swelling behavior of polyampholyte hydrogels.

Charge, orbital, and magnetic ordering in YBaFe2O5 from first-principles calculations

First principles calculations using the augmented plane wave plus local orbitals method, as implemented in the WIEN2k code, have been used to investigate the electronic and magnetic properties of YBaFe2O5, especially as regards the charge-orbital ordering. Although the total 3d charge disproportion is rather small, an orbital order parameter defined as the difference between t(2g) orbital occupations of Fe2+ and Fe3+ cations is large (0,73) and gives unambiguous evidence for charge and orbital ordering: Strong hybridization between O 2p and Fe e(g) states results in the nearly complete loss of the separation between the total charges at the Fe2+ and Fe3+ atoms.

The time delay in electrochemical measurements of a finite-volume system

For a sphere electrode enclosed in finite-volume electrolyte, the measured current will deviate from the result predicted by the semi-infinite diffusion theory after some time. By random-walk simulation, we compared this time to the one needed for diffusion layer to reach electrolyte boundary, and revealed a clear signal delay of electrochemical current. Further we presented a quantitative description of this delay time. The simulation results suggested that the semi-infinite diffusion theory can even be applied when the theoretical diffusion layer grows to 1.28 electrolyte thicknesses, with an accuracy better than 0.5%. We attributed this time delay to the molecules' finite propagation velocity. Finally, we discussed how this delay can influence and facilitate the following electrochemical detection towards the nanometer and single-cell scale.

Orbital ordering in Cs2AgF4 from first principles

First-principles calculations using the augmented plane wave plus local orbital method, as implemented in the WIEN2K code, have been used to investigate the structural, electronic, and magnetic properties of the layered perovskite Cs2AgF4. Our calculations indicate that an orthorhombic ground state for Cs2AgF4 is energetically favored over tetragonal. We also find that Cs2AgF4 should be a strong two-dimensional ferromagnet, with very weak antiferromagnetic coupling between the layers, in agreement with the experiment. More importantly, an antiferrodistortive ordering of z(2)-x(2) and z(2)-y(2) orbitals is inferred from the density of states and from a spin density isosurface analysis.

Studies of effect of phase volume ratio on transfer of ionizable species across the water/1,2-dichloroethane interface by a three-electrode setup

The electrochemical behavior of pyridine distribution at the water/1,2-dichloroethane interface with variable phase volume ratios (r=V-0/V-W) was investigated by cyclic voltammetry. The system was composed of an aqueous droplet supported on a Ag/AgCl disk electrode covered with an organic solution or an organic droplet supported on a Ag/AgTPBCl disk electrode covered with an aqueous solution. In this way, a conventional three-electrode potentiostat can be used to study an ionizable compound transfer process at a liquid/liquid interface with a wide range of phase volume ratios (from 0.0004 to 1 and from 1 to 2500). Using this special cell we designed, only very small volumes of both phase were needed for r equal to unity, which is very useful for the investigation of the distribution of ionizable species at a biphasic system when the available amount of species is limited. The ionic partition diagrams were obtained for different phase volume ratios.

Study of ionizable drugs transfer across the water/1,2-dichloroethane interface with phase volume ratio equal to unity using a three-electrode system

The electrochemical behavior of ionizable drugs (Amitriptyline, Diphenhydramine and Trihexyphenedyl) at the water/1,2-dichloroethane interface with the phase volume ratio (r = V-o/V-w) equal to 1 are investigated by cyclic voltammetry. The system is composed of an aqueous droplet supported at an Ag/AgCl disk electrode and it was covered with an organic solution. In this manner, a conventional three-electrode potentiostat can be used to study the ionizable drugs transfer process at a liquid/liquid interface. Physicochemical parameters such as the formal transfer potential, the Gibbs energy of transfer and the standard partition coefficients of the ionized forms of these drugs can be evaluated from cyclic voltammograms obtained. The obtained results have been summarized in ionic partition diagrams, which are a useful tool for predicting and interpreting the transfer mechanisms of ionizable drugs at the liquid/liquid interfaces and biological membranes.

Study of facilitated potassium ion transfer across a water vertical bar 1,2-dichloroethane interface using different phase volume ratio systems

A study of potassium ion transfer across a water \ 1,2-dichloroethane (W \ DCE) interface facilitated by dibenzo-18-crown-6 (DB18C6) with various phase volume ratio systems is presented. The key point was that a droplet of aqueous solution containing a redox couple, Fe(CN)(6)(3-)/Fe(CN)(6)(4-), with equal molar ratio, was first attached to a platinum electrode surface, and the resulting droplet electrode was then immersed into the organic solution containing a hydrophobic electrolyte to construct a platinum electrode/aqueous phase/organic phase system. The interfacial potential of the W \ DCE within the series could be externally controlled because the specific compositions in the aqueous droplet make the Pt electrode function like a reference electrode as long as the concentration ratio of Fe(CN)(6)(3-)/Fe(CN)(6)(4-) remains constant. In this way, a conventional three-electrode potentiostat can be used to study the ion transfer process at a liquid \ liquid (L \ L) interface facilitated by an ionophore with variable phase volume ratio (r = V-o/V-w). The effect of r on ion transfer and facilitated ion transfer was studied in detail experimentally. We also demonstrated that as low as 5 x 10(-8) M DB18C6 could be determined using this method due to the effect of the high phase volume ratio.

The glass transition temperatures of PS/PPO blends: Couchman volume-based equation and its verification

The glass transition temperatures (T-g) of PS/PPO blends with different compositions were studied under various pressures by means of a PVT-100 analyzer. A general relation of T-g and pressure of the PS/PPO system was deduced by fitting the experimental T-g's. Couchman volume-based equation was testified with the aid of those data. It was found that the experimental T-g's do not obey the Couchman equation of glass transition temperature based on thermodynamic theory. According to our studies, the major reason of the deviation is caused by the neglect of DeltaV(mix). (C) 2001 Published by Elsevier Science Ltd.

STUDY ON BONDING AND 4F ORBITAL EFFECT OF LANTHANIDE COMPOUNDS

The bonding and the 4f orbital effect of lanthanide elements at different valence state in their compounds have been studied by INDO method in this paper. The results obtained show that the bonding of lanthanide compounds is affected by many factors, such as valence state, ionic radius, ligand, coordinate number, space configuration etc. The strength of bonds composed of different ligands with lanthanide is distinctly different. The covalence of Ln-L bonds of lanthanide ions at high valence state in their compounds is larger than that at low valence state, The covalency at low coordinate number is larger than that at high coordinate number. Some lanthanide compounds with special configuration, besides sigma-bond, can form p(pi)-d(pi) dative bond with much overlap, which makes the Ln-L bond increase markedly. The effect of 4f orbitals on bonding is far less than that of 5d orbitals. The Ln 4f orbitals at 3 or 2 valence state may be considered to be essentially localized, while the contribution of 4f orbitals on bonding in 4 valent cerium compounds increases obviously, up to 1%.

黄土-红粘土化学风化与晚新生代气候变化——甘肃平凉白水剖面为例

Late Cenozoic has witnessed a series of climate-environmental change which ends with a transitional shift from greenhouse to icehouse conditions. In last two decades, scientists began to employ the tectonic uplift and its weathering effect to interpret the climatic changes during the late Cenozoic. However, this endeavor has partly been restricted by the lacking of regional and global chemical weathering data. The loess-red clay deposit in the Loess Plateau may record the weathering features of the detritus material from the wide range upwind of the Loess Plateau. Therefore geochemistry of the loess-plaeosol and red clay sequences may provide insights into the regional chemical weathering regime and the connection between the chemical weathering and the late Cenozoic climate-environmental change Here we selected 319 samples from the Baishui section near the Pingliang City, Gansu Province, and analyzed them with X-ray fluorescence. Based on the result, we reconstruct the chemical weathering history of the Baishui section since 6Ma. We chose CIA as the proxy for chemical weathering intensity. The CIA ratio in soil units is higher than in adjacent loess horizons, but lower than in the red clay, in good agreement with the field observation. The CIA ratios of the Baishui section correlates well with the global ice volume fluctuations, indicating that the global cooling may contribute a lot to the chemical weathering variations in Chinese Loess Plateau. There are at least 3 million-year time scale variations that can be identified in the chemical weathering intensity curve, i.e., between 3.3 to 2.1 Ma, 1.7 to 0.9 Ma and from 0.9Ma. We think these may reflect the combined effect of the tectonic uplift and ice sheets on monsoon intensity. Other time scale variations can be also observed. In the period between 2.4 and 0.8 Ma, the CIA record display the 400,000 years cycle, which may be resulted from the Tibetan uplift during the Pliocene-early Pleistocene which have significantly amplified the monsoon response sensitivity to the orbital-scale variations in insolation. From 1.2 Ma, the 100,000 years period became intensifying, and particularly after 0.8 Ma, the earlier monsoon response at 400,000 year periodicity was overwhelmed by the ice sheet forcing at 100,000 year periodicity. These may indicate that the expansions of the Northern Hemisphere ice sheets may have crossed a threshold, which enforce the monsoon responding at the 100,000 year periodicity.

中新世秦安黄土一古土壤序列记录的古气候变化周期

Analysis of periodic oscillations of climate is very important in understanding the behavior of the climate system. Milankovitch hypothesis, which holds that the glacial-interglacial climatic cycles during the Quaternary were primarily driven by variations in orbital parameters, has been supported by substantial geological evidence. Continuous long-term and high-resolution records are crucial to detect how variations of Earth's orbital parameters affected climate before the Quaternary when the boundary conditions were significantly different. Qinan loess formed in the Miocene is nearly continuous aeolian deposit in northern China. Previous study has established a constrained chronology, which provides a basis to examine long-term climatic variations. One of important issues to untangle the mechanisms behind major climate changes is the investigation of climate cycles recorded in Qinan loess. In this paper, two climatic proxies, magnetic susceptibility and redness, are analyzed for QA-I section to evaluate climate cycles using Maximum entropy spectral analysis and Blackman-Tuckey method. Main conclusions are presented as following: Results exhibit significant peaks at periods of 100 ka, 64 ka, 41 ka, 30 ka and 23 ka, but also 1000 ka, 600 ka and 400 ka. These peaks correspond to the dominant periods of the Earth's orbit parameters, which indicates that the formation of the aeolian sediment in northern China might be primarily driven by variations in orbital parameters. Fluctuations with different cycles respectively dominated in different periods. Major shifts in the dominant cycles occurred at 20.3, 19.0, 17.9, 15.2, 12.5 and 11.3 Myr ago. The transition that happened at 17.9 Myr ago was synchronous with the uplift of the Tibetan Plateau, while others at 15.2, 12.5 and 11.3 Myr ago were in good agreement with the timing of the development of Antarctic ice sheet. Therefore we inferred that these shifts might be related to changes in global ice volume and/or the Tibetan uplift. 3. The strong period of 100 ka is observed between 17.9 and 15.2, and 12.5 and 11.3 Myr ago. Ice sheet-climate models that have been used to explain the cause of the 100 ka period since the middle Pleistocene couldn't be responsible for driving the 100 ka climate cycle in the Miocene in Northern China because of the different boundary of climatic conditions between the Quaternary and Miocene. Further investigation is needed to understand how this cycle became dominant in Qinan loess records during these two time segments.