Photodynamics of Ga_(Zn)–V_(Zn) complex defect in Ga-doped ZnO

The wide-band-gap II–VI compound semiconductor ZnO is regarded as a promising single-photon emission(SPE)host material. In this work, we demonstrate that a(GaZn–VZn)-complex defect can readily be obtained and the density can be controlled in a certain range. In analogy to nitrogen vacancy centers, such a defect in ZnO is expected to be a new single photon source. The optical properties of the(GaZn–VZn)-complex defect are further studied by photoluminescence and time-resolved photoluminescence spectra measurements. The electron transitions between the defect levels emit light at ～ 650 nm with a lifetime of 10–20 nanoseconds, indicating a good coherent length for SPE. Finally, a two-level emitter structure is proposed to explain the carrier dynamics. We believe that the photodynamics study of the(GaZn–VZn)-complex defect in this work is important for ZnO-based quantum emitters.     

Synthesis and Reactivity of Mg(II)–Fe(II)–Fe(III) Hydroxycarbonates

Green rust-like compounds (GRs) were discovered as natural minerals in various hydromorphic soils, where anoxic conditions allow their stability. They may control some redox processes in aquifers and participate to the transformation of various pollutants. Since Mg(II) cations are present in the fields where GRs were discovered, a partial substitution of Mg(II) to Fe(II) leading to intermediate compounds between GRs and usual Mg(II)–Fe(III) hydroxysalts is suspected. Mg(II)–Fe(II)–Fe(II) hydroxycarbonates can be obtained as intermediate oxidation products of (Mg, Fe)(OH)₂ in carbonate-containing aqueous media obeying to [Fe^II _4(1–x)Mg^II _4x Fe^III ₂(OH)₁₂]²⁺ [CO₃ ^2– nH₂O]^–2. TMS spectra at 12 K are similar to those of GRs, i.e., two quadrupole doublets, one due to Fe(II) with a large isomer shift =1.29 mms^–1 (with respect to -iron at room temperature) and quadrupole splitting E _Q=2.76 mms^–1, the other one due to Fe(III) with smaller hyperfine parameters =0.49 mms^–1 and E _Q=0.44 mms^–1. Fe(II) ions oxidise rapidly into Fe(III) with dissolved O₂. The reactivity is similar to that of Fe(II)–Fe(III) hydroxysalts GR, and thus the potential of Mg(II)–Fe(II)–Fe(III) compounds for reducing pollutants.     

Transport properties in monolayer–bilayer–monolayer graphene planar junctions

The transport study of graphene based junctions has become one of the focuses in graphene research. There are two stacking configurations for monolayer–bilayer–monolayer graphene planar junctions. One is the two monolayer graphene contacting the same side of the bilayer graphene, and the other is the two-monolayer graphene contacting the different layers of the bilayer graphene. In this paper, according to the Landauer–Büttiker formula, we study the transport properties of these two configurations. The influences of the local gate potential in each part, the bias potential in bilayer graphene,the disorder and external magnetic field on conductance are obtained. We find the conductances of the two configurations can be manipulated by all of these effects. Especially, one can distinguish the two stacking configurations by introducing the bias potential into the bilayer graphene. The strong disorder and the external magnetic field will make the two stacking configurations indistinguishable in the transport experiment.     

Isospin breaking in the pion–nucleon scattering lengths

We analyze isospin breaking through quark mass differences and virtual photons in the pion–nucleon scattering lengths in all physical channels in the framework of covariant baryon chiral perturbation theory.     

Semiempirical assignment of the electron transitions in manganese(II)-doped II–VI compounds

The electron transitions in manganese(II)-doped II–VI compounds have been assigned by the Angular Overlap Model (AOM). The extracted AOM and electron repulsion parameters are applied to assess the covalency of the respective manganese-ligand bonds. A comparison with Crystal Field Theory (CFT) is made in order to demonstrate the advantages offered by the AOM. The Dq values for Mn(II) in CdS and CdSe were found by interpolation from the Dq vs R⁻⁵_ml relation.     

Resistance oscillations in junctions of superconductor–magnetic system

Resistance oscillations as a function of magnetic field were observed in superconductor–magnetic tunnel junctions of Nb–Fe–FeO_x–SiO₂–Au–Nb. Junctions involving superconductor–magnetic layer superconductor system are exciting because for certain regime of ferromagnetic layer thickness, a Josephson coupling with an intrinsic phase difference of π might be stabilized. For fabrication of the tunnel junctions the thin films were deposited by RF/DC magnetron sputtering. Using photolithography and reactive ion etching, square junctions of size varying from 50 μm to 250 μm were defined. I–V characteristics and R vs. H characteristics were studied at 4.2 K. When the magnetic field is applied parallel to the junction plane, measurements of the junction resistance as a function of magnetic field at a fixed temperature show resistance peaks whenever the total magnetic flux through the junction equals an integral multiple of flux quantum. The penetration depth of the superconducting electrodes was estimated from the positions of the resistance peaks.     

Gate-dependent photoresponse in self-assembled graphene p–n junctions

The intrinsic photocurrent generation mechanism of a self-assembled graphene p–n junction operating at 1.55 μm is investigated experimentally.It is concluded that both a photovoltage effect and a photothermoelectric effect contribute to the final photocurrent.The photocurrent signal at the p–n junction was found to be dominated by photothermoelectric current,arising from different self-assembled doping levels.     

Electron density characteristics and charge transfer effect of hydrogen bond O–H···Pt(II): atoms in molecules study and natural bond orbital analysis

In this report, we extended the works of Rizzato et al. [Angew. Chem. Int. Ed. 49, 7440 (2010)] on the nature of O–H···Pt hydrogen bond in trans-[PtCl₂(NH₃)(N–glycine)]·H₂O(1·H₂O) complex, by computational study of O–H···Pt interaction in [NBu₄][Pt(C₆F₅)₃(8-hydroxyquinaldine)], with emphasis on charge transfer effect in this interaction of platinum(II) and hydrogen atom. According to the crystallographic geometry reported by José María Casas et al., [NBu₄][Pt(C₆F₅)₃(8-hydroxyquinaldine)] possesses one O–H···Pt hydrogen bridging interaction, similar to the case in trans-[PtCl₂(NH₃)(N–glycine)]·H₂O(1·H₂O) complex. On the basis of topological criteria of electron density, we characterised this O–H···Pt interaction. Charge transferred between platinum(II) and σ^*_O–H orbital in this complex was calculated by using NBO method. The stabilised energy associated to charge transfer was estimated using a direct proportionality, that is 2–3 eV per electron transferred. Charge transfer effects in O–H···Pt hydrogen bonds were studied for these two complexes. Our results indicate that the interaction of O–H···Pt is closed–shell in nature with significant charge transfer, and that charge transfer effect is not negligible in the interaction of O–H···Pt. The second conclusion is different from the result of Rizzato et al.     

Influence of Copper(II) Ions on Radicals in DOPA–Melanin

DOPA–melanin (DOPA = 3,4-dihydroxyphenyl-alanine) complexes with Cu(II) cations were studied by electron paramagnetic resonance (EPR) spectroscopy. After the addition of metal cations to the melanin polymer, the EPR spectra parameters were measured. The axial g-factor values are g _|| = 2.20 and g _^ = 2.0 5 g_{ \bot } = 2.0 5 . Since $ g_{||} > g_{ \bot } > 2 $ g_{||} > g_{ \bot } > 2 , the ground state orbital of the unpaired electron of the Cu(II) complex is | x ²  -   y ² ñ \left| {{{x}}^{ 2} } \right. \, - \, \left. {{{y}}^{ 2} } \right\rangle . Square coordination of these cations in melanin is proposed. The influence of the Cu(II) concentration in solution used during synthesis on the concentration of melanin radicals was investigated. Cu(II) cations causes the decrease in the paramagnetic center concentration in melanin. The Cu(II) EPR spectra are not saturated within the microwave power range of 0.7–70 mW used in our experiment.     

Is the (hfac)Cu(I)–(tmvs) bond intrinsically weak?

Density functional theory studies were performed to study the structure and bonding of (hexafluoroacetylacetonate)-copper(I)-(trimethylvinylsilane) [Cu(hfac)(tmvs)], an ideal and important Cu(I)-CVD compound. A popular three-parameter hybrid density functional (B3LYP) with 6-311+G(d,p) and an effective core potential included LanL2DZ basis set was utilized for this purpose. The (hfac)Cu–(tmvs) bond energy of approximately 30?kcal?mol^?1 obtained at the B3LYP/6-311+G(d,p) level of theory reveals that the Cu–olefin bond in Cu(hfac)(tmvs) is not as weak as previously estimated/assumed and, hence, that the substrate plays a vital role in copper film formation from Cu(hfac)(tmvs). Bonding analysis reveals that fairly strong (hfac)Cu–(tmvs) bonding is the result of DCD-model σ-donation and π-back-bonding between the copper and tmvs in Cu(hfac)(tmvs).     

Tunneling conductance oscillations in spin–orbit coupled metal–insulator–superconductor junctions

The tunneling conductance for a device consisting of a metal–insulator–superconductor (MIS) junction is studied in presence of Rashba spin–orbit coupling (RSOC) via an extended Blonder–Tinkham–Klapwijk formalism. We find that the tunneling conductance as a function of an effective barrier potential that defines the insulating layer and lies intermediate to the metallic and superconducting electrodes, displays an oscillatory behavior. The tunneling conductance shows high sensitivity to the RSOC for certain ranges of this potential, while it is insensitive to the RSOC for others. Additionally, when the period of oscillations is an odd multiple of a certain value of the effective potential, the conductance spectrum as a function of the biasing energy demonstrates a contrasting trend with RSOC, compared to when it is not an odd multiple. The explanations for the observation can be found in terms of a competition between the normal and Andreev reflections. Similar oscillatory behavior of the conductance spectrum is also seen for other superconducting pairing symmetries, thereby emphasizing that the insulating layer plays a decisive role in the conductance oscillations of a MIS junction. For a tunable Rashba coupling, the current flowing through the junction can be controlled with precision.     

Waiting times of entangled electrons in normal–superconducting junctions

We consider a normal–superconducting junction in order to investigate the effect of new physical ingredients on waiting times. First, we study the interplay between Andreev and specular scattering at the interface on the distribution of waiting times of electrons or holes separately. In that case the distribution is not altered dramatically compared to the case of a single quantum channel with a quantum point contact since the interface acts as an Andreev mirror for holes. We then consider a fully entangled state originating from splitting of Cooper pairs at the interface and demonstrate a significant enhancement of the probability to detect two consecutive electrons in a short time interval. Finally, we discuss the electronic waiting time distribution in the more realistic situation of partial entanglement.     

Charge independence breaking and charge symmetry breaking in the nucleon–nucleon interaction from effective field theory

We discuss charge symmetry and charge independence breaking in an effective field theory approach for few-nucleon systems. We systematically introduce strong isospin-violating and electromagnetic operators in the theory. The charge dependence observed in the nucleon–nucleon scattering lengths is due to one-pion exchange and one electromagnetic four-nucleon contact term. This gives a parameter free expression for the charge dependence of the corresponding effective ranges, which is in agreement with the rather small and uncertain empirical determinations. We also compare the low energy phase shifts of the nn and the np system. We present a classification scheme for corrections to the leading order results and show that power counting explains previously made phenomenological observations.     

Red-Emitting Ru(II) Metal–Ligand Complexes

A series of Ru(N–N)₂(dcbp or mcmabp) complexes were synthesized where N-N represents a diimine ligand, dcbp is 4,4-dicaboxylic 2,2-bipyridine, and mcmabp is 4,4-2,2-bipyridine monocarboxy amide. The N-N ligand was either 2,2-bipyridine (bpy), 4,4-dimethyl-2,2-bipyridine (dmbp), or 4,4,5,5-tetramethyl-2,2-bipyridine (tmbp). We observed a red shift in both the absorption and emission with the presence of dcbp in the mixed ligand complex when compared to Ru(bpy)₃. Conversion of one of the carboxylic groups in dcbp to amide resulted in further red shifts. A red shift in the absorption and the emission was also observed with increasing numbers of electrons donating methyl substitutions on bpy. The lifetimes of the complexes decreased as expected with the red shift emission. The tris heteroleptic Ru (tmphen)(tmbp)(dcbp or mcmabp) were the most red-shifted among the complexes. Because of the red shift in the absorption, the maxima in the fundamental anisotropies of the mixed ligand Ru complexes are now coincident with the maxima in the absorption. Overall we have been able to make an Ru complex which emits at about 700 nm in all aqueous environment and has a lifetime of about 220 ns.     

On Bose–Einstein condensation in Josephson junctions star graph arrays

We report on the evidence of anomalous currents in graph-shaped arrays of Josephson junctions along peculiar branches of the networks. The specific case of a star-shaped array is considered and the evidence of the anomalies is achieved by comparing the current-voltage characteristics of the arrays embedded in the star structure with those of “reference” arrays which are fabricated by-side the network structure and are dc-isolated from these. The experimental data are consistent with the results of a theoretical model predicting gradients of the populations of Cooper pairs on the islands situated in proximity of the central superconductive island as a result of a Bose–Einstein condensation process.     

Obvious variation of rectification behaviors induced by isomeric anchoring groups for dipyrimidinyl–diphenyl molecular junctions

The rectifying properties modulated by isomeric anchoring groups of dipyrimidinyl–diphenyl co-oligomer diodes sandwiched between two gold electrodes are investigated using density functional theory combined with the nonequilibrium Green?s function method. Our results show that the rectifying behaviors of the co-oligomer diode are significantly modulated by isomeric substitution of anchoring groups. When the isomeride nitrile end group is replaced by the isocyanide one, for symmetric arrangement of electrodes, the rectifying direction shows obvious inversion for the isocyanide–diblock–thiol junction, and the rectification ratio is obviously enhanced for the thiol–diblock–isocyanide junction. The influence on rectification induced by asymmetric electrodes is also discussed. The analysis of the transmission spectra and the molecular projected self-consistent Hamiltonian under various external bias voltages gives inside mechanisms of the observed results.     

Photon-assisted tunneling versus tunneling of excited electrons in metal–insulator–metal junctions

Photocurrent measurements in Ag–Al₂O₃–Al metal–insulator–metal junctions under illumination with ultra-short laser pulses reveal that tunneling and internal photoemission of excited electrons are the dominating transport mechanisms. Photon-assisted tunneling is observed under rare conditions that depend critically on the preparation of the interface. The comparison of time-resolved two-pulse correlation measurements with model calculations shows that the photon-induced transport of excited electrons is well described using a one-dimensional many-particle model for two coupled metallic leads, whereas a single-particle model for nonresonant excitation in a rectangular double-minimum potential reveals the signature of photon-assisted tunneling. PACS 73.40.-c; 72.10.-d; 73.40.Gk; 73.50.Pz     

Metal–ligand bond directionality in the M2–NH3 complexes (M = Cu,Ag and Au)

The metal–ligand bonds in the M₂–NH₃ complexes (M = Au, Ag and Cu) are directional and the M–M–N angles tend to be linear. Natural energy decomposition analysis (NEDA) and localised molecular orbital energy decomposition analysis (LMOEDA) approaches indicate that the metal-ligand bonds in these complexes are mainly electrostatic in nature, however, the electrostatic is not the cause of the linearity of M–M–N arrangements. Instead, NEDA shows that the charge transfer and core repulsion are mainly responsible for the directionality of these bonds. In the LMOEDA point of view, the repulsion term is the main reason for the linearity of these complexes. Interacting quantum atoms (IQA) analysis shows that inter-atomic and inter-fragment interactions favour the nonlinear arrangements; however, these terms are compensated by the atomic self-energies, which stabilise the linear structure.