High-fidelity simulations of CdTe vapor deposition from a new bond-order potential-based molecular dynamics method

CdTe has been a special semiconductor for constructing the lowest-cost solar cells and the CdTe-based Cd1-xZnxTe alloy has been the leading semiconductor for radiation detection applications. The performance currently achieved for the materials, however, is still far below the theoretical expectations. This is because the property-limiting nanoscale defects that are easily formed during the growth of CdTe crystals are difficult to explore in experiments. Here we demonstrate the capability of a bond order potential-based molecular dynamics method for predicting the crystalline growth of CdTe films during vapor deposition simulations. Such a method may begin to enable defects generated during vapor deposition of CdTe crystals to be accurately explored

Cobalt-Porphyrin Catalyzed Electrochemical Reduction of Carbon Dioxide in Water II: Mechanism from First Principles

We apply first principles computational techniques to analyze the two-electron, multi-step, electrochemical reduction of CO2 to CO in water using cobalt porphyrin as a catalyst. Density Functional Theory calculations with hybrid functionals and dielectric continuum solvation are used to determine the steps at which electrons are added. This information is corroborated with ab initio molecular dynamics simulations in an explicit aqueous environment which reveal the critical role of water in stabilizing a key intermediate formed by CO2 bound to cobalt. Using potential of mean force calculations, the intermediate is found to spontaneously accept a proton to form a carboxylate acid group at pH<9.0, and the subsequent cleavage of a C-OH bond to form CO is exothermic and associated with a small free energy barrier. These predictions suggest that the proposed reaction mechanism is viable if electron transfer to the catalyst is sufficiently fast. The variation in cobalt ion charge and spin states during bond breaking, DFT+U treatment of cobalt 3d orbitals, and the need for computing electrochemical potentials are emphasized.Comment: 33 pages, 7 figure

Evidence for O-atom exchange in the O(^1D) + N_2O reaction as the source of mass-independent isotopic fractionation in atmospheric N_2O

Recent experiments have shown that in the oxygen isotopic exchange reaction for O(^1D) + CO_2 the elastic channel is approximately 50% that of the inelastic channel [Perri et al., 2003]. We propose an analogous oxygen atom exchange reaction for the isoelectronic O(^1D) + N_2O system to explain the mass-independent isotopic fractionation (MIF) in atmospheric N_2O. We apply quantum chemical methods to compute the energetics of the potential energy surfaces on which the O(^1D) + N_2O reaction occurs. Preliminary modeling results indicate that oxygen isotopic exchange via O(^1D) + N_2O can account for the MIF oxygen anomaly if the oxygen atom isotopic exchange rate is 30–50% that of the total rate for the reactive channels

XUV Opacity of Aluminum between the Cold-Solid to Warm-Plasma Transition

We present calculations of the free-free XUV opacity of warm, solid-density aluminum at photon energies between the plasma frequency at 15 eV and the L-edge at 73 eV, using both density functional theory combined with molecular dynamics and a semi-analytical model in the RPA framework with the inclusion of local field corrections. As the temperature is increased from room temperature to 10 eV, with the ion and electron temperatures equal, we calculate an increase in the opacity in the range over which the degree of ionization is constant. The effect is less pronounced if only the electron temperature is allowed to increase. The physical significance of these increases is discussed in terms of intense XUV-laser matter interactions on both femtosecond and picosecond time-scales.Comment: 4 pages, 3 figure