Electronic structure of UF_5

Non-relativistic and relativistic self-consistent Hartree- Fock-Slater and Dirac-Slater models have been used to calculate one-electron energy levels and ionization energies for UF_5. The calculations were performed in an assumed structure of C_4v symmetry with the uranium atom at the center of mass of the molecule. The spacing and level ordering are compared with earlier results obtained with the MS X\alpha method using the muffin-tin approximation. Connections with the multiphoton isotope separation scheme of UF_6 are discussed.

Theoretical study of the physicochemical properties of the light transactinides

A theoretical study of the physicochemical properties of elements 104, 105, and 106 and their compounds in the gas phase and aqueous solutions has been undertaken using relativistic atomic and molecular codes. Trends in properties such as bonding, ionization potentials, electron affinities, energies of electronic transitions, stabilities of oxidation states etc. have been defined within the corresponding chemical groups and within the transactinides. These trends are shown to be determined by increasing relativistic effects within the groups. The behaviour of some gas phase compounds and complexes in solutions is predicted for the gas chromatography and solvent extraction experiments. Redox potentials in aqueous solutions of these elements are estimated.

Redox reactions of group 5 elements, including element 105, in aqueous solutions

Standard redox potentials E^0(M^z+x/M^z+) in acidic solutions for group 5 elements including element 105 (Ha) and the actinide, Pa, have been estimated on the basis of the ionization potentials calculated via the multiconfiguration Dirac-Fock method. Stability of the pentavalent state was shown to increase along the group from V to Ha, while that of the tetra- and trivalent states decreases in this direction. Our estimates have shown no extra stability of the trivalent state of hahnium. Element 105 should form mixed-valence complexes by analogy with Nb due to the similar values of their potentials E^0(M^3+/M^2+). The stability of the maximumoxidation state of the elements decreases in the direction 103 > 104 > 105.

Prediction of some thermodynamic properties of selected compounds of element 104

A set of parametrized equations has been published by Bratsch and Lagowski for calculating thermodynamic properties of the lanthanides, actinides, element 104, and certainrelated elements. Since these equations were applied to element 104, new values for the first four ionization energies and radii of the ions of charge +1, +2, +3, and +4 have been calculated for this element. The parametrized equations are used here with these new values to calculate some thermodynamic properties of element 104.

Predicted properties of the superheavy elements. III. Element 115, Eka-Bismuth

Element 115 is expected to be in group V-a of the periodic table and have most stable oxidation states of I and III. The oxidation state of I, which plays a minor role in bismuth chemistry, should be a major factor in 115 chemistry. This change will arise because of the large relativistic splitting of the spherically symmetric 7p_l/2 shell from the 7P_3/2 shell. Element 115 will therefore have a single 7p_3/2 electron outside a 7p^2_1/2 closed shell. The magnitude of the first ionization energy and ionic radius suggest a chemistry similar to Tl^+. Similar considerations suggest that 115^3+ will have a chemistry similar to Bi^3+. Hydrolysis will therefore be easy and relatively strongly complexing anions of strong acids will be needed in general to effect studies of complexation chemistry. Some other properties of 115 predicted are as follows: ionization potentials I 5.2 eV, II 18.1 eV, III 27.4 eV, IV 48.5 eV, 0 \rightarrow 5^+ 159 eV; heat of sublimation, 34 kcal (g-atom)^-1; atomic radius, 2.0 A; ionic radius, 115^+ 1.5 A, 115^3+ 1.0 A; entropy, 16 cal deg^-1 (g-atom)^-l (25°); standard electrode potential 115^+ |115, -1.5 V; melting and boiling points are similar to element 113.

Relativistic effects in physics and chemistry of element 105. [Part] IV.

Results of relativistic (Dirac-Slater and Dirac-Fock) and nonrelativistic (Hartree-Fock-Slater) atomic and molecular calculations have been compared for the group 5 elements Nb, Ta, and Ha and their compounds MCl_5, to elucidate the influence of relativistic effects on their properties especially in going from the 5d element Ta to the 6d element Ha. The analysis of the radial distribution of the valence electrons of the metals for electronic configurations obtained as a result of the molecular calculations and their overlap with ligands show opposite trends in behavior for ns_1/2, np_l/2, and (n -1 )d_5/2 orbitals for Ta and Ha in the relativistic and nonrelativistic cases. Relativistic contraction and energetic stabilization of the ns_1/2 and np_l/2 wave functions and expansion and destabilization of the (n-1)d_5/2 orbitals make hahnium pentahalide more covalent than tantalum pentahalide and increase the bond strength. The nonrelativistic treatment of the wave functions results in an increase in ionicity of the MCl_5 molecules in going from Nb to Ha making element Ha an analog of V. Different trends for the relativistic and nonrelativistic cases are also found for ionization potentials, electronic affinities, and energies of charge-transfer transitions as well as the stability of the maximum oxidation state.

Relativistic molecular calculations of superheavy molecules

Relativistic molecular calculations within the Dirac-Slater scheme have been used in a study of the electronic structure of 6d-metal superheavy hexafluorides. The theoretical results are compared with calculations and measurements of the homolog 4d- and 5d-metal hexafluorides. Large spin-orbit splitting dominates the electronic structure and even has the same order of magnitude as the crystal-field splitting for the valence electrons for the superheavy molecules. Ionization energies have been calculated using a transition state procedure.

Femtosecond spectroscopy of molecular autoionization and fragmentation

Femtosecond laser pulses are applied to the study of the dynamics and the pathways of multiphoton-induced ionization, autoionization, and fragmentation of Na_2 in molecular-beam experiments. In particular, we report on first results obtained studying electronic autoionization (leading to Na_2{^+} + {e ^-}) and autoionization-induced fragmentation (leading to Na{^+} + Na + {e ^-}) of a bound doubly excited molecular state. The final continuum states are analyzed by photoelectron spectroscopy and by measuring the mass and the released kinetic energy of the corresponding ionic fragments with a time-of-flight arrangement.

Time-resolved studies of neutral and ionized Na_n clusters with femtosecond light pulses

The real-time dynamics of Na_n (n=3-21) cluster multiphoton ionization and fragmentation has been studied in beam experiments applying femtosecond pump-probe techniques in combination with ion and electron spectroscopy. Three dimensional wave packet motions in the trimer Na_3 ground state X and excited state B have been observed. We report the first study of cluster properties (energy, bandwidth and lifetime of intermediate resonances Na_n^*) with femtosecond laser pulses. The observation of four absorption resonances for the cluster Na_8 with different energy widths and different decay patterns is more difficult to interpret by surface plasmon like resonances than by molecular structure and dynamics. Timeresolved fragmentation of cluster ions Na_n^+ indicates that direct photo-induced fragmentation processes are more important at short times than the statistical unimolecular decay.

Molecular photochemistry with femtosecond laser pulses

Femtosecond laser pulses generated from an amplified coiliding pulse modelocked ring dye laser have been employed in molecular beam experiments to study the dynamics and the pathways of multiphoton induced ionization, autoionization and fragmentation of Na2 . Energy distributions of photoelectrons arising from these processes and the mass and released kinetic energy of the corresponding fragment ions are measured by time-of-flight spectroscopy.

Fundamental interactions of molecules (Na_2, Na_3) with intense femtosecond laser pulses

The real-time dynamics of multiphoton ionization and fragmentation of molecules Na_2 and Na_3 has been studied in molecular beam experiments employing ion and electron spectroscopy together with femtosecond pump-probe techniques. Experiments with Na_2 and Na_3 reveal unexpected features of the dynamics of the absorption of several photons as seen in the one- and three-dimensional vibrational wave packet motion in different potential surfaces and in high laser fields: In Na_2 a second major resonance-enhanced multiphoton ionization (REMPI) process is observed, involving the excitation of two electrons and subsequent electronic autoionization. The possibility of controlling a reaction by controlling the duration of propagation of a wave packet on an electronically-excited surface is demonstrated. In high laser fields, the contributions from direct photoionization and from the second REMPI process to the total ion yield change, due to different populations in the electronic states participating in the multiphoton ionization (MPI) processes. In addition, a vibrational wave packet motion in the electronic ground state is induced through stimulated emission pumping by the pump laser. The 4^1 \summe^+_g shelf state of Na_2 is given as an example for performing frequency spectroscopy of highlying electronic states in the time domain. Pure wave packet effects, such as the spreading and the revival of a vibrational wave packet, are investigated. The three-dimensional wave packet motion in the Na_3 reflects the normal modes in the X and B states, and shows in addition the pseudorotational motion in the B state in real time.

Femtosecond dynamics of molecules and clusters

The real-time dynamics of multiphoton ionization and fragmentation of molecules - Na_2 , Na_3 - and clusters - Na_n, Hg_n - has been studied in molecular beam experiments employing ion and electron spectroscopy together with femtosecond pump-probe techniques. Experiments with Na_2 and Na_3 reveal unexpected features of the dynamics of the absorption of several photons as seen in the one- and three dimensional vibrational wave packet motion in different potential surfaces and in high laser fields. Cluster size dependent studies of physical properties such as absorption resonances, lifetimes and decay channels have been performed using tunable femtosecond light pulses in resonance enhanced multiphoton ionization (REMPI) of the cluster size under investigation. This method failed in ns-laser experiments due to the ultrafast decay of the studied cluster. For Na_n, cluster we find that for cluster sizes n \le 21 molecular excitations and properties prevail over collective excitations of plasmon-like resonances. In the case of Hg_n cluster prompt formation of singly and doubly charged cluster are observed up to n \approx 60. The transient multiphoton ionization spectra show a 'short' time wave packet dynamics, which is identical for singly and doubly charged mercury clusters while the 'long' time fragmentation dynamics is different.

Quo vadis, Philosoph und Philosophin ?

Diese Arbeit sucht nach den Erwerbstätigkeiten und Kompetenzen deutscher Philosophie-Absolvent(inn)en und nach der Wahrheit ihrer angeblichen Arbeitslosenquote. Anhand von EU-Papieren werden Anknüpfungspunkte für kompetenzorientierte Philosophie-Lehre aufgezeigt. Es wird dargestellt, wie Philosoph(inn)en die Kompetenzdiskussion sowohl in Deutschland als auch – über die OECD – international beeinfluss(t)en und mit gestalt(et)en. Die notwendige Voraussetzung für Lernen und Kompetenzentwicklung ist die Plastizität unseres Gehirnes. Biographisch beginnt das Lernen in der Schule und findet sein vorläufiges Ende in der Arbeitswelt. Diese Arbeit versucht, den zwischen schul- und arbeitsweltorientierten Kompetenzforschern bestehenden Graben zu überwinden. Problemlösefähigkeit in internationalen Teams wird für die gelingende Zukunft unserer Welt als wesentliche fachübergreifende Kompetenz erachtet. Für den in Deutschland sehr einflussreichen Kompetenzforscher John Erpenbeck ist die Selbstorganisationsfähigkeit ein Ankerpunkt. Für den Entwickler der noch heute in Deutschland anerkannten Kompetenzbereiche (Sach-, Sozial- und Selbstkompetenz), Heinrich Roth, liegt die "Höchstform menschlicher Handlungsfähigkeit" in der moralischen Selbstbestimmung. Die Zukunft wird zeigen, inwieweit das Verständnis von Regeln, Werten und Normen bei den arbeitswissenschaftlichen Kompetenzforschern im Korsett einer jeweiligen Unternehmensphilosophie verbleibt, oder inwieweit die Selbstorganisationsfähigkeit im Sinne einer moralischen Selbstbestimmung des Einzelnen die Unternehmensphilosophie prägt. In literaturhistorischen Anhängen wird ein assoziatives Feld von Einzelinformationen dargeboten, die einen roten Faden im Sinne eines sich aufbauenden Argumentes vermissen lassen. Vordergründig wird nur ein loses Band von John Dewey und William James bis Heinrich Roth und die heutige Zeit hergestellt. Hintergründig will der Autor darauf hinweisen, dass es einen Unterschied macht, ob sich der Begriff "Selbstorganisationsfähigkeit" aus einer physikalischen oder einer biologischen Wurzel entwickelt. Der Autor sieht keinen zwingenden Grund für das Bestehen eines eigenständigen Studienganges "Philosophie". Allerdings kann er auch nicht erkennen, warum er abgeschafft werden sollte.

Molecular Imaging using Strong-Field Processes

Die Arbeit befasst sich mit dem Zusammenhang zwischen einfachen Molekülen und deren Verhalten in starken, kurzen Laserfeldern. Einerseits wird versucht, strukturelle Daten des Moleküls in den Elektronen- und Photonenspektren wiederzuerkennen. Andererseits geht es darum, ein Bild der elektronischen Wellenfunktion aus den spektralen Daten abzuleiten.

An Interpolative Analytical Cache Model with Application to Performance-Power Design Space Exploration

Caches are known to consume up to half of all system power in embedded processors. Co-optimizing performance and power of the cache subsystems is therefore an important step in the design of embedded systems, especially those employing application specific instruction processors. In this project, we propose an analytical cache model that succinctly captures the miss performance of an application over the entire cache parameter space. Unlike exhaustive trace driven simulation, our model requires that the program be simulated once so that a few key characteristics can be obtained. Using these application-dependent characteristics, the model can span the entire cache parameter space consisting of cache sizes, associativity and cache block sizes. In our unified model, we are able to cater for direct-mapped, set and fully associative instruction, data and unified caches. Validation against full trace-driven simulations shows that our model has a high degree of fidelity. Finally, we show how the model can be coupled with a power model for caches such that one can very quickly decide on pareto-optimal performance-power design points for rapid design space exploration.