Predicted formation of superconducting platinum-hydride crystals under pressure in the presence of molecular hydrogen

Noble metals adopt close-packed structures at ambient pressure and rarely undergo structural transformation at high pressures. Platinum (Pt) is normally considered to be unreactive and is therefore not expected to form hydrides under pressure. We predict that platinum hydride (PtH) has a lower enthalpy than its constituents solid Pt and molecular hydrogen at pressures above 21.5?GPa. PtH transforms to a hexagonal close-packed or face-centered cubic (fcc) structure between 70 and 80 GPa. Linear response calculations indicate that PtH is a superconductor at these pressures with a critical temperature of about 10-25?K. These findings help to shed light on recent observations of pressure-induced metallization and superconductivity in hydrogen-rich materials. We show that the formation of fcc noble metal hydrides under pressure is common and examine the possibility of superconductivity in these materials.     

Quantum Monte Carlo study of the first-row atoms and ions

Quantum Monte Carlo calculations of the first-row atoms Li-Ne and their singly positively charged ions are reported. Multideterminant-Jastrow-backflow trial wave functions are used which recover more than 98% of the correlation energy at the variational Monte Carlo level and more than 99% of the correlation energy at the diffusion Monte Carlo level for both the atoms and ions. We obtain the first ionization potentials to chemical accuracy. We also report scalar relativistic corrections to the energies, mass-polarization terms, and one- and two-electron expectation values.     

Study of structural and electronic transport properties of Ce-doped LaMnO3

The structural and electronic transport properties of La_1−x Ce _x MnO₃ (x=0.0–1.0) have been studied. All the samples exhibit orthorhombic crystal symmetry and the unit cell volume decreases with Ce doping. They also make a metal-insulator transition (MIT) and transition temperature increases with increase in Ce concentration up to 50% doping. The system La_0.5Ce_0.5MnO₃ also exhibits MIT instead of charge-ordered state as observed in the hole doped systems of the same composition.     

Quantum Monte Carlo calculations of the dissociation energy of the water dimer

We report diffusion quantum Monte Carlo (DMC) calculations of the equilibrium dissociation energy D(e) of the water dimer. The dissociation energy measured experimentally, D(0), can be estimated from D(e) by adding a correction for vibrational effects. Using the measured dissociation energy and the modern value of the vibrational energy Mas et al., [J. Chem. Phys. 113, 6687 (2000)] leads to D(e)=5.00+/-0.7 kcal mol(-1), although the result Curtiss et al., [J. Chem. Phys. 71, 2703 (1979)] D(e)=5.44+/-0.7 kcal mol(-1), which uses an earlier estimate of the vibrational energy, has been widely quoted. High-level coupled cluster calculations Klopper et al., [Phys. Chem. Chem. Phys. 2, 2227 (2000)] have yielded D(e)=5.02+/-0.05 kcal mol(-1). In an attempt to shed new light on this old problem, we have performed all-electron DMC calculations on the water monomer and dimer using Slater-Jastrow wave functions with both Hartree-Fock approximation (HF) and B3LYP density functional theory single-particle orbitals. We obtain equilibrium dissociation energies for the dimer of 5.02+/-0.18 kcal mol(-1) (HF orbitals) and 5.21+/-0.18 kcal mol(-1) (B3LYP orbitals), in good agreement with the coupled cluster results.     

Identification of isomeric flavonoid glucuronides in urine and plasma by metal complexation and LC-ESI-MS/MS

Noncovalent complexes were used for structural determination and isomer differentiation of flavonoid glucuronides. Several flavonoid glucuronides including naringenin-7-O-glucuronide, synthesized here for the first time, were used as test compounds. Electrospray ionization quadrupole ion trap mass spectrometry with collision-induced dissociation (CID) was used to analyze complexes of the form [Co(II) (L-H) (Aux)]+ and [Co(II) (L-H) (Aux)2]+, in which L is the flavonoid glucuronide and Aux is a phenanthroline-based ligand. These complexes yielded characteristic fragmentation patterns that facilitated assignment of the substitution position of the glucuronides. The methods were adapted to liquid chromatography/tandem mass spectrometry (LC-MS/MS) with postcolumn cobalt complexation and were tested on extracts from biological fluids. The metabolites naringenin-7-O-glucuronide and naringenin-4'-O-glucuronide were detected in human urine following the consumption of grapefruit juice. Isomeric quercetin glucuronides were identified and differentiated after spiking rat plasma at the 1 microM level, proving that the new methods are effective at biologically relevant concentrations.     

Electron emission from diamondoids: a diffusion quantum Monte Carlo study

We present density-functional theory (DFT) and quantum Monte Carlo (QMC) calculations designed to resolve experimental and theoretical controversies over the optical properties of H-terminated C nanoparticles (diamondoids). The QMC results follow the trends of well-converged plane-wave DFT calculations for the size dependence of the optical gap, but they predict gaps that are 1-2 eV higher. They confirm that quantum confinement effects disappear in diamondoids larger than 1 nm, which have gaps below that of bulk diamond. Our QMC calculations predict a small exciton binding energy and a negative electron affinity (NEA) for diamondoids up to 1 nm, resulting from the delocalized nature of the lowest unoccupied molecular orbital. The NEA suggests a range of possible applications of diamondoids as low-voltage electron emitters.     

Fourier Transform Spectroscopy of the A'(1)Pi-X(1)Sigma(+) System of CaO

The A'(1)Pi-X(1)Sigma(+) near-infrared system of CaO was observed for the first time at high resolution using a Fourier transform spectrometer. The A'(1)Pi-X(1)Sigma(+) chemiluminescence was excited in a Ca + N(2)O flame produced in a Broida-type oven. More than 3000 rotational lines, classified into 19 bands involving the A'(1)Pi 0 /= 2) levels with the nearby b(3)Sigma(+) (v-2) levels has been detected. An extended set of A'(1)Pi (v = 0-3) data has been obtained which is suitable for use in a future multistate deperturbation analysis of the a(3)Pi approximately A'(1)Pi approximately b(3)Sigma(+) approximately A(1)Sigma(+) complex of excited states. The new near-infrared spectra of the A'(1)Pi-X(1)Sigma(+) transition of CaO also permits the first direct high-resolution linkage between the orange and green systems and the near-infrared bands. Copyright 2000 Academic Press.     

Internal kink instability during off-axis electron cyclotron current drive in the DIII-D tokamak

Experimental evidence is reported of an internal kink instability driven by a new mechanism: barely trapped suprathermal electrons produced by off-axis electron cyclotron heating on the DIII-D tokamak. It occurs in plasmas with an evolving safety factor profile q(r) when q(min) approaches 1. This instability is most active when ECCD is applied on the high field side of the flux surface. It has a bursting behavior with poloidal/toroidal mode number = m/n = 1/1. In positive magnetic shear plasmas, this mode becomes the fishbone instability. This observation can be qualitatively explained by the drift reversal of the barely trapped suprathermal electrons.     

Apparent spin polarization decay in Cu-dusted Co/Al2O3/Co tunnel junctions

Co/Al2O3/Co magnetic tunnel junctions with an interfacial Cu layer have been investigated with in situ growth characterization and ex situ magnetotransport measurements. Cu interlayers grown on Co give an approximately exponential decay of the tunneling magnetoresistance with xi approximately 0.26 nm while those grown on Al2O3 have a decay length of 0.70 nm. The difference in decay lengths can be explained by different growth morphologies, and in this way clarifies a present disagreement in the literature. For monolayer coverage of Cu, we show that the tunneling spin polarization is suppressed by at least a factor of 2 compared to Co and beyond approximately 5 ML it becomes vanishingly small.