ELECTRONIC-STRUCTURES OF THE ALKALI-CONTAINING BUCKMINSTERFULLERENES (A-DELTA-C60) (A=LI,NA,K,RB,CS) AND THE HALOGEN-CONTAINING BUCKMINSTERFULLERENES (H-DELTA-C60) (H=F,CL,BR,I)

The geometrical parameters and electronic structures of C60, (A partial derivative C60) (A = Li, Na, K, Rb, Cs) and (H partial derivative C60) (H = F, Cl, Br, I) have been calculated by the EHMO/ASED (atom superposition and electron delocalization) method. When putting a central atom into the C60 cage, the frontier and subfrontier orbitals of (A partial derivative C60) (A = Li, Na, K, Rb, Cs) and (H partial derivative C60) (H = F, Cl) relative to those of C60 undergo little change and thus, from the viewpoint of charge transfer, A (A = Li, Na, K, Rb, Cs) and H (H = F, Cl) are simply electron donors and acceptors for the C60 cage resPeCtively. Br is an electron acceptor but it does influence the frontier and subfrontier MOs for the C60 cage, and although there is no charge transfer between I and the C60 cage, the frontier and subfrontier MOs for the C60 cage are obviously influenced by I. The stabilities DELTAE(X) (DELTAE(X) = (E(X) + E(C60)) - E(x partial derivative C60)) follow the sequence I < Br < None < Cl < F < Li < Na < K < Rb < Cs while the cage radii r follow the inverse sequence. The stability order and the cage radii order have been explained by means of the (exp-6-1) potential.

Magnetic and electronic properties of CaCu3Cr4O12 and CaCu3Cr2Sb2O12 by first-principles density functional calculation

The electronic and magnetic properties of CaCu3Cr4O12 and CaCu3Cr2Sb2O12 are investigated by the use of the full-potential linearized augumented plane wave (FPLAPW) method. The calculated results indicate that CaCu3- Cr4O12 is a ferrimagnetic and half-metallic compound, in good agreement with previous theoretical studies. CaCu3- Cr2Sb2O12 is a ferrimagnetic semiconductor with a small gap of 0.136 eV. In both compounds, because Cr4+ 3d (d(2)) and Cr3+ 3d (d(3)) orbitals are less than half filled, the coupling between Cr-Cu is antiferromagnetic, whereas that between Cu-Cu and Cr-Cr is ferromagnetic. The total net spin moment is 5.0 and 3.0 mu(B) for CaCu3Cr4O12 and CaCu3Cr2Sb2O12, respectively. In CaCu3Cr4O12, the 3d electrons of Cr4+ are delocalized, which strengthens the Cr-Cr ferromagnetic coupling. For CaCu3Cr2Sb2O12, the doping of nonmagnetic ion Sb5+ reduces the Cr-Cr ferromagnetic coupling, and the half-filled Cr3+ t(2g) (t(2g)(3)) makes the chromium 3d electrons localized. In addition, the ordering arrangement of the octahedral chromium and antimony ions also prevents the delocalization of electrons. Hence, CaCu3Cr2Sb2O12 shows insulating behavior, in agreement with the experimental observation.

Electronic entanglement purification scheme enhanced by charge detections

We present an entanglement purification scheme for the mixed entangled states of electrons with the aid of charge detections. Our scheme adopts the electronic polarizing beam splitters rather than the controlled-NOT (CNOT) operations, but the total successful probability of our scheme can reach the quantity as large as that of the the CNOT-operation-based protocol and twice as large as that of linear-optics-based protocol for the purification of photonic entangled states. Thus our scheme can achieve a high successful prabability without the usage of CNOT operations.

Polaronic correction to the first excited electronic energy level in an anisotropic semiconductor quantum dot

Within the framework of second-order Rayleigh-Schrodinger perturbation theory, the polaronic correction to the first excited state energy of an electron in an quantum dot with anisotropic parabolic confinements is presented. Compared with isotropic confinements, anisotropic confinements will make the degeneracy of the excited states to be totally or partly lifted. On the basis of a three-dimensional Frohlich's Hamiltonian with anisotropic confinements, the first excited state properties in two-dimensional quantum dots as well as quantum wells and wires can also be easily obtained by taking special limits. Calculations show that the first excited polaronic effect can be considerable in small quantum dots.

Ultrafast electronic excitation in CaF2 crystals

A new pump and probe experimental system was developed, the pump pulse duration of which is stretched and is much longer than that of the probe pulse. Using this system, time-resolved electronic excitation processes and damage mechanisms in CaF2 crystals were studied. The measured reflectivity of the probe pulse begins to increase at the peak of the pump pulse and increases rapidly in the latter half of the pump pulse, when the pump pulse duration is stretched to 580fs. Our experimental results indicate that both multiphoton ionization and impact ionization play important roles in the generation of conduction band electrons, at least they do so when the pump pulse durations are equal to or longer than 580fs.

Electrochemical fabrication and electronic behavior of polypyrrole nano-fiber array devices

Electrochemically active Polypyrrole (PPy) nano-fiber array device was fabricated via electrochemical deposition method using aluminum anodic oxide (AAO) membrane as template. After alkaline treatment electrochemically active PPy nano-fiber lost electrochemical activity, and became electrochemically inactive PPy. The electronic properties of PPy nano-fiber array devices were measured by means of a simple method. It was found that for an indium-tin oxide/electrochemically inactive PPy nano-fiber device, the conductivity of nano-fiber increased with the increase of voltage applied on the two terminals of nano-fiber. The electrochemical inactive PPy nano-fiber might be used as a nano-fiber switching diode. Both Au/electrochemically active PPy and Au/electrochemically inactive PPy nano-fiber devices demonstrate rectifying behavior, and might have been used for further application as nano-rectifiers. (c) 2005 Elsevier B.V. All tights reserved.

First-principles study of the electronic structures and absorption spectra for the PbMoO4 crystal with lead vacancy

The electronic structures and absorption spectra for the perfect PbMoO4 crystal and the crystal containing lead vacancy V-Pb(2-) with lattice structure optimized are calculated using density functional theory code CASTEP. The calculated absorption spectra of the PbMoO4 crystal containing V-Pb(2-) exhibit three absorption bands peaking at 2.0 eV (620 nm), 3.0 eV (413 run) and 3.3 eV (375 nm), which are in good agreement with experimental values. The theory predicts that the 390 nm, 430 nm and 580 run absorption bands are related to the existence of V-Pb(2-) in the PbMoO4 crystal.

First-principles calculations of electronic structures and absorption spectra of YAlO3 crystals with F center

National Nature Science Foundation of China (Grant No. 60607015)

Bioaccumulative characteristics of hexabromocyclododecanes in freshwater species from an electronic waste recycling area in China

Hexabromocyclododecanes (HBCDs) are now emerging ubiquitous contaminants due to their wide usage, persistence and toxicities. To investigate the bioaccumulative characteristics of HBCDs, sediments, Winkle (Littorina littorea), crucian carp (Carassius carassius) and loach (Misgurnus anguillicaudatus) were collected from two streams near an E-waste dismantling site in China. and HBCD exposure test was then conducted on Chinese rare minnow. The concentration of HBCDs was 14 ng g(-1) dry weight in sediments, 186. 377 and 1791 ng g(-1) lipid weight in winkle, crucian carp and loach, respectively. gamma-HBCD was found to be the dominant diastereoisomer in the sediments (63% of total HBCDs). However, alpha-HBCD was selectively accumulated in the biotic samples and contributed to 77%, 63% and 63% of total HBCDs in winkle, crucian carp and loach, respectively. Moreover, an enrichment of (-)-enantiomers of alpha- and gamma-HBCD were found in the winkle. The reverse results were observed in the crucian carp and loach. Similar observations of diastereoisomeric and enantiomeric composition were obtained in Chinese rare minnow with those found in the crucian carp and loach. These results indicate that the freshwater species from the streams are contaminated by HBCDs. alpha-HBCD can be selectively accumulated in organisms and the accumulative characteristics are enantioselective among species. (C) 2009 Elsevier Ltd. All rights reserved.

Elevated levels of urinary 8-hydroxy-2'-deoxyguanosine in male electrical and electronic equipment dismantling workers exposed to high concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans, polybrominated diphenyl ethers, and polychlorinated biphenyls

To investigate the occupational exposure levels to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polybrominated diphenyl ethers (PBDEs), and polychlorinated biphenyls (PCBs), indoor dust (n = 3) in workshops and hair samples from male workers (n = 64) were collected at two electrical and electronic equipment waste (E-waste) dismantling factories located in the LQ area in east China in July 11-13, 2006. Pre- and postworkshift urines (64 of each) were also collected from the workers to study oxidative damage to DNA using 8-hydroxy-2'-deoxyguanosine (8-OHdG) as a biomarker. The concentrations of PCDD/Fs, PCDD/F-WHO-TEQs, PBDEs, PCBs and PCB-WHO-TEQs were (50.0 +/- 8.1) x 10(3), 724.1 +/- 249.6, (27.5 +/- 5.8) x 10(6), (1.6 +/- 0.4) x 10(9), (26.2 +/- 3.0) x 10(3) pg/g dry weight (dw) in dust, and (2.6 +/- 0.6) x 10(3), 42.4 +/- 9.3, (870.8 +/- 205.4) x 10(3), (1.6 +/- 0.2) x 10(6), 41.5 +/- 5.5 pg/g dw in hair, respectively. The homologue and congener profiles in the samples demonstrated that high concentrations of PCDD/Fs, PBDEs, and PCBs were originated from open burning of E-waste. The 8-OHdG levels were detected at 6.40 +/- 1.64 mu mol/mol creatinine in preworkshift urines. However, the levels significantly increased to 24.55 +/- 5.96 mu mol/mol creatinine in postworkshift urines (p < 0.05). Then, it is concluded that there is a high cancer risk originated from oxidative stress indicated by the elevated 8-OHdG levels in the E-waste dismantling workers exposed to high concentrations of PCDD/Fs, PBDEs, and PCBs.

Body loadings and health risk assessment of polychlorinated dibenzo-p-dioxins and dibenzofurans at an intensive electronic waste recycling site in China

This study is one of the very few investigating the dioxin body burden of a group of child-bearing-aged women at an electronic waste (e-waste) recycling site (Taizhou, Zhejiang Province) (24 +/- 2.83 years of age, 40% were primiparae) and a reference site (Lin'an city, Zhejiang Province, about 245 km away from Taizhou) (24 +/- 2.35 years of age, 100% were primiparae) in China. Five sets of samples (each set consisted of human milk, placenta, and hair) were collected from each site. Body burdens of people from the e-waste processing site (human milk, 21.02 +/- 13.81 pg WHO-TEQ(1998/g) fat (World Health Organization toxic equivalency 1998); placenta, 31.15 +/- 15.67 pg WHO-TEQ(1998/g) fat; hair, 33.82 +/- 17.74 pg WHO-TEQ(1998/g) dry wt) showed significantly higher levels of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurnas (PCDD/Fs) than those from the reference site (human milk, 9.35 +/- 7.39 pg WHO-TEQ(1998/g) fat, placenta, 11.91 +/- 7.05 pg WHO-TEQ(1998/g) fat; hair, 5.59 +/- 4.36 pg WHO-TEQ(1998/g) dry wt) and were comparatively higher than other studies. The difference between the two sites was due to e-waste recycling operations, for example, open burning, which led to high background levels. Moreover, mothers from the e-waste recycling site consumed more foods of animal origin. The estimated daily intake of PCDD/Fs within 6 months by breast-fed infants from the e-waste processing site was 2 times higher than that from the reference site. Both values exceeded the WHO tolerable daily intake for adults by at least 25 and 11 times, respectively. Our results implicated that e-waste recycling operations cause prominent PCDD/F levels in the environment and in humans. The elevated body burden may have health implications for the next generation.

Biotransfer of persistent organic pollutants from a large site in China used for the disassembly of electronic and electrical waste

Samples of groundwater, river water, river sediment, paddy soil, rice seeds, hen eggs, fish, umbilical cord blood, and newborn meconium were collected from October 2002 to October 2003 near a large site in China used for the disassembly of obsolete transformers and other electronic or electrical waste. Six indicator PCB congeners, three non-ortho dioxin-like PCB congeners, and six organochlorine pesticides were determined in the samples by GC with electron capture detector. The results demonstrated that the local environment and edible foods had been seriously polluted by toxic PCBs and organochlorine pesticides. The actual daily intakes (ADIs) of these pollutants were estimated for local residents living in the area. The intake data showed that the contents of PCBs in these local residents were substantial, as the ADI estimates greatly exceed the reference doses set by the World Health Organization and the United States Agency for Toxic Substances and Disease Registry. The presence of the indicator PCB congeners in the cord blood and the meconium samples, as well as significant correlations (r(2) > 0.80, p < 0.05) between these levels, suggests a potential biotransfer of these indicators from mothers to their newborns. This preliminary study showed that obsolete transformers and other electronic or electrical waste can be an important source for the emission of persistent organic pollutants into the local environment, such as through leakage, evaporation, runoff, and leaching. Contamination from this source appears to have reached the level considered to be a serious threat to environmental and human health around the disassembly site.

Quantum Confinement Effects and Electronic Properties of SnO2 Quantum Wires and Dots

On the basis of the density functional theory (DFT) within local density approximations (LDA) approach, we calculate the band gaps for different size SnO2 quantum wire (QWs) and quantum dots (QDs). A model is proposed to passivate the surface atoms of SnO2 QWs and QDs. We find that the band gap increases between QWs and bulk evolve as Delta E-g(wire) = 1.74/d(1.20) as the effective diameter d decreases, while being Delta E-g(dot) = 2.84/d(1.26) for the QDs. Though the similar to d(1.2) scale is significantly different from similar to d(2) of the effective mass result, the ratio of band gap increases between SnO2 QWs and QDs is 0.609, very close to the effective mass prediction. We also confirm, although the LDS calculations underestimate the band gap, that they give the trend of band gap shift as much as that obtained by the hybrid functional (PBE0) with a rational mixing of 25% Fock exchange and 75% of the conventional Perdew-Burke-Ernzerhof (PBE) exchange functional for the SnO2 QWs and QDs. The relative deviation of the LDA calculated band gap difference Lambda E-g compared with the corresponding PBE0 results is only within 5%. Additionally, it is found the states of valence band maximum (VBM) and conduction band minimum (CBM) of SnO2 QWs or QDs have a mostly p- and s-like envelope function symmetry, respectively, from both LDA and PBE0 calculations.

First-principles LDA plus U and GGA plus U study of neptunium dioxide

We have performed a systematic first-principles investigation to calculate the electronic structures, mechanical properties, and phonon-dispersion curves of NpO2. The local-density approximation+U and the generalized gradient approximation+U formalisms have been used to account for the strong on-site Coulomb repulsion among the localized Np 5f electrons. By choosing the Hubbard U parameter around 4 eV, the orbital occupancy characters of Np 5f and O 2p are in good agreement with recent experiments [A. Seibert, T. Gouder, and F. Huber, J. Nucl. Mater. 389, 470 (2009)]. Comparing to our previous study of ThO2, we note that stronger covalency exists in NpO2 due to the more localization behavior of 5f electrons of Np in line with the localization-delocalization trend exhibited by the actinides series.