Detection of autocatalytic decomposition behavior of energetic materials using APTAC

Characterization of autocatalytic decomposition reactions is important for the safe handling and storage of energetic materials. Isothermal differential scanning calorimetry (DSC) has been widely used to detect autocatalytic decomposition of energetic materials. However, isothermal DSC tests are time consuming and the choice of experimental temperature is crucial. This paper shows that an automatic pressure tracking calorimeter (APTAC) can be a reliable and efficient screening tool for the identification of autocatalytic decomposition behavior of energetic materials. Hydroxylamine nitrate (HAN) is an important member of the hydroxylamine family. High concentrations of HAN are used as liquid propellants, and low concentrations of HAN are used primarily in the nuclear industry for decontamination of equipment. Because of its instability and autocatalytic decomposition behavior, HAN has been involved in several incidents.     

Experimental observations of a left-handed material that obeys Snell's law

We measure two-dimensional profiles of collimated microwave beams transmitted through composite wire and split-ring resonator prisms. Prior experiments suggest these structures have a negative index of refraction, though these claims have been questioned. Our 2D measurements demonstrate that transmission obeys Snell's law with a negative index, confirming the refractive nature of this signal and refuting alternatives posed in the criticisms. In addition, we present preliminary evidence that a flat rectangular slab of this material can focus power from a point source.     

Ultrafast magneto-optics in nickel: magnetism or optics?

Several magnetic and optical processes contribute to the magneto-optical response of nickel thin films after excitation by a femtosecond laser pulse. We achieved a first complete identification by explicitly measuring the time-resolved Kerr ellipticity and rotation, as well as its temperature and magnetic field dependence in epitaxially grown (111) and (001) oriented Cu/Ni/Cu wedges. The first hundreds of femtoseconds the response is dominated by state filling effects. The true demagnetization takes approximately 0.5-1 ps. At the longer (sub-ns) time scales the spins are found to precess in their anisotropy field. Simple and transparent models are introduced to substantiate our interpretation.     

Tunable coupling in circuit quantum electrodynamics using a superconducting charge qubit with a V-shaped energy level diagram

We introduce a new type of superconducting charge qubit that has a V-shaped energy spectrum and uses quantum interference to provide independently tunable qubit energy and coherent coupling to a superconducting cavity. Dynamic access to the strong coupling regime is demonstrated by tuning the coupling strength from less than 200 kHz to greater than 40 MHz. This tunable coupling can be used to protect the qubit from cavity-induced relaxation and avoid unwanted qubit-qubit interactions in a multiqubit system.     

Kondo effect in the presence of magnetic impurities

We measure transport through gold grain quantum dots fabricated using electromigration, with magnetic impurities in the leads. A Kondo interaction is observed between dot and leads, but the presence of magnetic impurities results in a gate-dependent zero-bias conductance peak that is split due to a RKKY interaction between the spin of the dot and the static spins of the impurities. A magnetic field restores the single Kondo peak in the case of an antiferromagnetic RKKY interaction. This system provides a new platform to study Kondo and RKKY interactions in metals at the level of a single spin.     

Theoretical Prediction and Explanation of Reaction Site Selectivity in the Addition of a Phenoxy Group to Perfluoropyrimidine,Perfluoropyridazine, and Perfluoropyrazine

Perfluoroaromatics, such as perfluoropyridine and perfluorobenzene, are privileged synthetic scaffolds in organofluorine methodology, undergoing a series of regioselective substitution reactions with a variety of nucleophiles. This unique chemical behavior allows for the synthesis of many perfluoroaromatic derived molecules with unique and diverse architectures. Recently, it has been demonstrated that perfluoropyridine and perfluorobenzene can be utilized as precursors for a variety of materials, ranging from high performance polyaryl ethers to promising drug scaffolds. In this work, using density functional theory, we investigate the possibility of perfluoropyrimidine, perfluoropyridazine, and perfluoropyrazine participating in similar substitution reactions. We have found that the first nucleophilic addition of a phenoxide group substitution on perfluoropyrimidine and on perfluoropyridazine would happen at a site para to one of the nitrogen atoms. While previous literature points to mesomeric effects as the primary cause of this phenomenon, our work demonstrates that this effect is enhanced by the fact that the transition states for these reactions result in bond angles that allow the phenoxide to π-complex with the electron-deficient diazine ring. The second substitution on perfluoropyrimidine and on perfluoropyridazine is most likely to happen at the site para to the other nitrogen. The second substitution on perfluoropyrazine is most likely to happen at the site para to the first substitution. The activation energies for these reactions are in line with those reported for perfluoropyridine and suggest that these platforms may also be worth investigation in the lab as possible monomers for high performance polymers.