Calculation of gamma spectra for positron annihilation on molecules

Calculations of gamma spectra for positron annihilation for a selection of molecules, including methane and its fluoro-substitutes, ethane, propane, butane and benzene are presented. The contribution to the ?-spectra from individual molecular orbitals is obtained from electron momentum distributions calculated using the density functional theory (DFT) based B3LYP/TZVP model. For positrons thermalised to room temperature, the calculation, in its simplest form, effectively treats the positron as a plane wave and gives positron annihilation ?-spectra linewidths that are broader (30-40%) than experiment, although the main chemical trends are reproduced. The main physical reason for this is the neglect of positron repulsion from the nuclei. We show that this effect can be incorporated through momentum-dependent correction factors, determined from positron-atom calculations, e.g., many-body perturbation theory. Inclusion of these factors in the calculation gives linewidths that are in improved agreement with experiment.

Calculations for doubly-excited states populated in two-electron processes

Recent calculations of doubly-excited states for two and four-electron states in neutral atoms and ions are described. In particular the radiative properties of these states are considered. It is pointed out that some of these states live so long that triply-excited states perhaps can be formed in neutralisation processes at surfaces. © 1991 Springer-Verlag.

yambo: An ab initio tool for excited state calculations

yambo is an ab initio code for calculating quasiparticle energies and optical properties of electronic systems within the framework of many-body perturbation theory and time-dependent density functional theory. Quasiparticle energies are calculated within the GW approximation for the self-energy. Optical properties are evaluated either by solving the Bethe-Salpeter equation or by using the adiabatic local density approximation. yambo is a plane-wave code that, although particularly suited for calculations of periodic bulk systems, has been applied to a large variety of physical systems. yambo relies on efficient numerical techniques devised to treat systems with reduced dimensionality, or with a large number of degrees of freedom. The code has a user-friendly command-line based interface, flexible 110 procedures and is interfaced to several publicly available density functional ground-state codes.

Quasiparticle calculations of the electronic properties of ZrO2 and HfO2 polymorphs and their interface with Si

Quasiparticle calculations are performed to investigate the electronic band structures of various polymorphs of Hf and Zr oxides. The corrections with respect to density-functional-theory results are found to depend only weakly on the crystal structure. Based on these bulk calculations as well as those for bulk Si, the effect of quasiparticle corrections is also investigated for the band offsets at the interface between these oxides and Si assuming that the lineup of the potential at the interface is reproduced correctly within density-functional theory. On the one hand, the valence-band offsets are practically unchanged with a correction of a few tenths of electron volts. On the other hand, conduction-band offsets are raised by 1.3-1.5 eV. When applied to existing calculations for the offsets at the density-functional-theory level, our quasiparticle corrections provide results in good agreement with the experiment.

On the required shape corrections to the local density and generalized gradient approximations to the Kohn-Sham potentials for molecular response calculations of (hyper)polarizabilities and excitation energies

It is well known that shape corrections have to be applied to the local-density (LDA) and generalized gradient (GGA) approximations to the Kohn-Sham exchange-correlation potential in order to obtain reliable response properties in time dependent density functional theory calculations. Here we demonstrate that it is an oversimplified view that these shape corrections concern primarily the asymptotic part of the potential, and that they affect only Rydberg type transitions. The performance is assessed of two shape-corrected Kohn-Sham potentials, the gradient-regulated asymptotic connection procedure applied to the Becke-Perdew potential (BP-GRAC) and the statistical averaging of (model) orbital potentials (SAOP), versus LDA and GGA potentials, in molecular response calculations of the static average polarizability alpha, the Cauchy coefficient S-4, and the static average hyperpolarizability beta. The nature of the distortions of the LDA/GGA potentials is highlighted and it is shown that they introduce many spurious excited states at too low energy which may mix with valence excited states, resulting in wrong excited state compositions. They also lead to wrong oscillator strengths and thus to a wrong spectral structure of properties like the polarizability. LDA, Becke-Lee-Yang-Parr (BLYP), and Becke-Perdew (BP) characteristically underestimate contributions to alpha and S-4 from bound Rydberg-type states and overestimate those from the continuum. Cancellation of the errors in these contributions occasionally produces fortuitously good results. The distortions of the LDA, BLYP, and BP spectra are related to the deficiencies of the LDA/GGA potentials in both the bulk and outer molecular regions. In contrast, both SAOP and BP-GRAC potentials produce high quality polarizabilities for 21 molecules and also reliable Cauchy moments and hyperpolarizabilities for the selected molecules. The analysis for the N-2 molecule shows, that both SAOP and BP-GRAC yield reliable energies omega(i) and oscillator strengths f(i) of individual excitations, so that they reproduce well the spectral structure of alpha and S-4.(C) 2002 American Institute of Physics.