Application of time and temperature resolved x-ray diffraction (TRXRD) to thermal analysis

The application of TRXRD for thermal analysis is demonstrated using examples of phase transitions, solid-state reactions and high-temperature corrosion. The measuring system produces a series of diffraction patterns, which are evaluated by a difference procedure that a reduces the data to curves comparable to DSC and TG curves and thus suited to kinetic evaluation.     

Fractional revivals in the rovibrational motion of I2

Motivated by pump-probe experiments of I(2) in a room-temperature sample, the detection of fractional revivals is investigated using full-dimensional quantum wave packet calculations. It is shown that the structures observed in the pump-probe signal depend sensitively on the probe parameters employed and that the observed signal reflects a particular phase effect between fractional revivals.     

On perturbations of linear m-accretive operators on reflexive Banach spaces

In this note we prove some results on the m-accretivity of sums and products of linear operators. In particular we obtain the following theorem: LetA, B be two m-accretive operators on a reflexive Banach space. IfA is invertible and (A)^–1 B is accretive thenBA ^–1 andA+B are m-accretive.     

Low energy excitations in KMnO4 with 1 eV<=ΔE<=10 eV from electron-energy loss spectroscopy

Electron-energy loss spectra of potassium permanganate (KMnO₄) with primary electron energies 25 eV<=E₀<=500 eV show 7 peaks in the energy-loss range 1 eV<=ΔE<=10eV and are successfully analysed with a superposition of 7 independent Gaussians. The intensity of these lines follow roughly a power-law dependence on the primary energy I∝E ₀ ^-α . There are two groups of lines, the first with an exponent α≈0.5, while the lines in the second group decay much stronger with increasingE ₀ corresponding to a value 0.9<=α<=1.3. The 4 lines in the first group are identified as dipole allowed transitions by comparison to recent first principle molecular-orbital calculations for the (MnO₄) molecule by H. Nakai et al. The dipole-allowed excitation spectrum obtained from this analysis agrees very well with these first principle calculations.     

The structure of magnesium alanate

Mg(AlH(4))(2) was produced as a nanocrystalline powder by metathesis of NaAlH(4) and MgCl(2). Starting with a structure estimation which was developed from an evaluation of FTIR data and comparison of structural properties of two solvent adducts, quantum chemical calculations were performed on the density functional theory (DFT) level. The calculated atomic positions were used to simulate an X-ray powder diffraction pattern, based on a trigonal unit cell. The simulated pattern was congruent to experimental data. Thus, magnesium alanate exhibits a CdI(2) layer structure, the layers being formed by Mg atoms occupying the Cd sites and AlH(4) tedrahedra occupying the sites of the iodine atoms in CdI(2).     

Asymptotic properties of the exchange energy density and the exchange potential of finite systems: relevance for generalized gradient approximations

It is shown that generalized gradient approximations (GGAs) for exchange only, due to their very limited form, quite generally can not simultaneously reproduce both the asymptotic forms of the exchange energy density and the exchange potential of finite systems. Furthermore, mechanisms making GGAs formally approach at least one of these asymptotic forms do not improve the corresponding quantity in the relevant part of the asymptotic regime of atoms. By constructing a GGA which leads to superior atomic exchange energies compared to all GGAs heretofore but does not reproduce the asymptotic form of the exact exchange energy density it is demonstrated that this property is not important for obtaining extremely accurate atomic exchange energies. We conclude that GGAs by their very concept are not suited to reproduce these asymptotic properties of finite systems. As a byproduct of our discussion we present a particularly simple and direct proof of the well known asymptotic structure of the exchange potential of finite spherical systems.