Over-the-Gap Conductance Oscillations in Superconducting Vanadium Nanocontacts Induced by Hydrogen Impurities.

We have investigated the current-voltage (I-V) characteristics of Josephson junctions made by a low-temperature superconductor of vanadium (V) with a small amount of hydrogen (H) and deuterium (D) impurities using a mechanically controllable break junction (MCBJ) technique. Below the superconducting transition temperature TC, the differential conductance dI/dV spectra show distinct peaks within the superconducting gap, known as the subgap structure, which result from multiple Andreev reflections in pure V nanocontacts. Additionally, the H and D impurities in V nanocontacts induce several new conductance peaks outside the gap, referred to as an over-the-gap structures (OGSs). We found that the OGS peaks exhibit strong temperature dependence until the temperature is close to TC and follow the gap function predicted by BCS theory. When the contact diameter is changed at low temperature using the MCBJ technique, the OGS anomalies change almost linearly with the inverse of the contact diameter. In addition, the gap anomalies are significantly shifted outward by changing the positions of the H atoms through application of a high bias voltage between the contacts. The above features suggest that the OGS peaks are caused by the superconducting quasiparticle interference induced by H or D impurities and/or inhomogeneous structures in the nanocontacts.

Temperature dependence of spherical electron transfer in a nanosized [Fe14] complex.

The study of transition metal clusters exhibiting fast electron hopping or delocalization remains challenging, because intermetallic communications mediated through bridging ligands are normally weak. Herein, we report the synthesis of a nanosized complex, [Fe(Tp)(CN)3]8[Fe(H2O)(DMSO)]6 (abbreviated as [Fe14], Tp-, hydrotris(pyrazolyl)borate; DMSO, dimethyl sulfoxide), which has a fluctuating valence due to two mobile d-electrons in its atomic layer shell. The rate of electron transfer of [Fe14] complex demonstrates the Arrhenius-type temperature dependence in the nanosized spheric surface, wherein high-spin centers are ferromagnetically coupled, producing an S = 14 ground state. The electron-hopping rate at room temperature is faster than the time scale of Mössbauer measurements (<~10-8 s). Partial reduction of N-terminal high spin FeIII sites and electron mediation ability of CN ligands lead to the observation of both an extensive electron transfer and magnetic coupling properties in a precisely atomic layered shell structure of a nanosized [Fe14] complex.