A hydrothermal reactor has been used for surface doping of anatase TiO2 nanoparticles (∼ 13 nm across) with Eu3+ ions in aqueous fluids to 370 °C and ∼20 MPa. XRD and Raman measurements made both before and after hydrothermal treatment with Eu show that the anatase structure of the TiO2 nanoparticles (NPs) is preserved. SEM imaging, combined with XRD indicates that the size and overall morphology of the TiO2 nanoparticles is preserved subsequent to hydrothermal treatment in the presence of Eu. The photoluminescence occurring in the 400 to ∼700 nm range of the (as prepared) Eu surface-doped TiO2 NPs are red-shifted by ∼ 50 nm and reduced in intensity relative to the photoluminescence of TiO2 NPs.

The synthesis of titanium and zirconium complexes ligated by bidentate “salicylaldimine-like” N-heterocyclic carbenes (NHCs) is reported. These complexes are rare examples of group IV transition metal NHC adducts. In the presence of methylaluminoxane these complexes are useful initiators for the polymerization of ethylene and the copolymerization of ethylene with norbornene and 1-octene. Linear high density polyethylene could be produced. The Ti complexes are also utilized to yield highly syndiotactic polystyrene.

A methodology is described for atomistic simulations of shock-compressed materials that incorporates quantum nuclear effects on the fly. We introduce a modification of the multi-scale shock technique (MSST) that couples to a quantum thermal bath described by a colored noise Langevin thermostat. The new approach, which we call QB-MSST, is of comparable computational cost to MSST and self-consistently incorporates quantum heat capacities and Bose-Einstein harmonic vibrational distributions. As a first test, we study shock-compressed methane using the ReaxFF potential. The Hugoniot curves predicted from the new approach are found comparable with existing experimental data. We find that the self-consistent nature of the method results in the onset of chemistry at 40% lower pressure on the shock Hugoniot than observed with classical molecular dynamics. The temperature change associated with quantum heat capacity is determined to be the primary factor in this shift.

A thorough understanding of chemistry in extreme environments is a major challenge in experimental as well as theoretical work. With continual improvements in ultrafast optical measurements and new methods for simulations of shock-induced chemistry for timescales approaching a nanosecond, the opportunity is beginning to exist to connect experiments with simulations on the same timescale. In the present work, we compute the optical properties of the energetic material nitromethane (CH3NO2) for the first 100 picoseconds behind the detonation shock front in a molecular dynamics simulation. We compute optical spectra using the Kubo-Greenwood approach with DFT Kohn-Sham electronic states and compare with spectra computed by linear-response time-dependent density functional theory (TDDFT). The latter typically yields more accurate spectra for molecular systems. At optical wavelengths, the TDDFT method offers a correction of up to 25% in the real part of conductivity relative to the Kubo-Greenwood calculation. We also study the effects of thermal electronic excitations on the calculated spectra, and find no discernible change at optical wavelengths. In all of our calculations, we observe a non-monotonic change over time in the entire spectrum of optical properties as decomposition products evolve. The most optically relevant decomposition products are found to be NO, CNO, CNOH, water, and larger transient molecules. In particular, the disappearance of transient NO and CNO molecules (about 90 picoseconds behind the shock front) is coincident with a substantial decrease in conductivity across the optical spectrum.

High pressure low temperature electrical resistance measurements were carried out on a series of 122 iron-based superconductors using a designer diamond anvil cell. These studies were complemented by image plate x-ray diffraction measurements under high pressures and low temperatures at beamline 16-BM-D, HPCAT, Advanced Photon Source. A common feature of the 1-2-2 iron-based materials is the observation of anomalous compressibility effects under pressure and a Tetragonal (T) to Collapsed Tetragonal (CT) phase transition under high pressures. Specific studies on antiferromagnetic spin-density-wave Ba0.5Sr0.5Fe2As2 and Ba(Fe0.9Ru0.1)2As2 samples are presented to 10 K and 41 GPa. The collapsed tetragonal phase was observed at a pressure of 14 GPa in Ba0.5Sr0.5Fe2As2 at ambient temperature. The highest superconducting transition temperature in Ba0.5Sr0.5Fe2As2 was observed to be at 32 K at a pressure of 4.7 GPa. The superconductivity was observed to be suppressed on transformation to the CT phase in 122 materials.