Energetic photoionization of neutral and ionic metal clusters

We show, with an example of Na_92, that for jellium metal clusters the interference of fast electron-waves emitted from equivalent sites on the cluster edge produces monochromatic oscillations in all photoionization observables as a function of the photoelectron momentum; the effect is equivalent to the usual dispersion phenomenon. In dealing with formalisms, a serious consequence of the inadequacy of self-interaction corrected local density-functional theory in correctly accounting for the exchange interaction is identified. We also briefly discuss the influence of the ionicity of the residual core on photospectra by considering the neutral member with N=58 and and the ionic member with N=52 of the Na_58 iso-jellium series, where N is the number of valence electrons. A few final remarks on possible implications of these results on other quantum systems of delocalized electrons are made.Comment: 4 pages, 5 figures, for XIII-NCAMP (IACS-Calcutta, India) proceeding

Fragmentation phase transition in atomic clusters I --- Microcanonical thermodynamics

Here we first develop the thermodynamics of microcanonical phase transitions of first and second order in systems which are thermodynamically stable in the sense of van Hove. We show how both kinds of phase transitions can unambiguously be identified in relatively small isolated systems of $\sim 100$ atoms by the shape of the microcanonical caloric equation of state $$ I.e. within microcanonical thermodynamics one does not need to go to the thermodynamic limit in order to identify phase transitions. In contrast to ordinary (canonical) thermodynamics of the bulk microcanonical thermodynamics (MT) gives an insight into the coexistence region. The essential three parameters which identify the transition to be of first order, the transition temperature $T_{tr}$, the latent heat $q_{lat}$, and the interphase surface entropy $\Delta s_{surf}$ can very well be determined in relatively small systems like clusters by MT. The phase transition towards fragmentation is introduced. The general features of MT as applied to the fragmentation of atomic clusters are discussed. The similarities and differences to the boiling of macrosystems are pointed out.Comment: Same as before, abstract shortened my e-mail address: [email protected]

Effect of disorder on transport properties in a tight-binding model for lead halide perovskites

The hybrid organic-inorganic lead halide perovskite materials have emerged as remarkable materials for photovoltaic applications. Their strengths include good electric transport properties in spite of the disorder inherent in them. Motivated by this observation, we analyze the effects of disorder on the energy eigenstates of a tight-binding model of these materials. In particular, we analyze the spatial extension of the energy eigenstates, which is quantified by the inverse participation ratio. This parameter exhibits a tendency, and possibly a phase transition, to localization as the on-site energy disorder strength is increased. However, we argue that the disorder in the lead halide perovskites corresponds to a point in the regime of highly delocalized states. Our results also suggest that the electronic states of mixed-halide materials tend to be more localized than those of pure materials, which suggests a weaker tendency to form extended bonding states in the mixed-halide materials and is therefore not favourable for halide mixing.Comment: 24 pages (preprint), 11 figure

Spurious oscillations from local self-interaction correction in high energy photoionization calculations for metal clusters

We find that for simple metal clusters a single-electron description of the ground state employing self-interaction correction (SIC) in the framework of local-density approximation strongly contaminates the high energy photoionization cross sections with spurious oscillations for a subshell containing node(s). This effect is shown connected to the unphysical structure that SIC generates in ensuing state-dependent radial potentials around a position where the respective orbital density attains nodal zero. Non-local Hartree-Fock that exactly eliminates the electron self-interaction is found entirely free from this effect. It is inferred that while SIC is largely unimportant in high photon-energies, any implementation of it within the local frame can induce unphysical oscillations in the high energy photospectra of metal clusters pointing to a general need for caution in choosing appropriate theoretical tools

Fragmentation Phase Transition in Atomic Clusters II - Coulomb Explosion of Metal Clusters -

We discuss the role and the treatment of polarization effects in many-body systems of charged conducting clusters and apply this to the statistical fragmentation of Na-clusters. We see a first order microcanonical phase transition in the fragmentation of $Na^{Z+}_{70}$ for Z=0 to 8. We can distinguish two fragmentation phases, namely evaporation of large particles from a large residue and a complete decay into small fragments only. Charging the cluster shifts the transition to lower excitation energies and forces the transition to disappear for charges higher than Z=8. At very high charges the fragmentation phase transition no longer occurs because the cluster Coulomb-explodes into small fragments even at excitation energy $\epsilon^* = 0$.Comment: 19 text pages +18 *.eps figures, my e-mail adress: [email protected] submitted to Z. Phys.

Ultrafast Transfer and Transient Entrapment of Photoexcited Mg Electron in Mg@C-60

Electron relaxation is studied in endofullerene Mg@C-60 after an initial localized photoexcitation in Mg by nonadiabatic molecular dynamics simulations. Two approaches to the electronic structure of the excited electronic states are used: (i) an independent particle approximation based on a density-functional theory description of molecular orbitals and (ii) a configuration-interaction description of the many-body effects. Both methods exhibit similar relaxation times, leading to an ultrafast decay and charge transfer from Mg to C-60 within tens of femtoseconds. Method (i) further elicits a transient trap of the transferred electron that can delay the electron-hole recombination. Results shall motivate experiments to probe these ultrafast processes by two-photon transient absorption or photoelectron spectroscopy in gas phase, in solution, or as thin films