Analytische Ableitungen der Energie für den "Equation-of-Motion-Coupled-Cluster"-Ansatz zur Berechnung von Ionisationspotentialen

In der vorliegenden Arbeit wird die Theorie der analytischen zweiten Ableitungen für die EOMIP-CCSD-Methode formuliert sowie die durchgeführte Implementierung im Quantenchemieprogramm CFOUR beschrieben. Diese Ableitungen sind von Bedeutung bei der Bestimmung statischer Polarisierbarkeiten und harmonischer Schwingungsfrequenzen und in dieser Arbeit wird die Genauigkeit des EOMIP-CCSD-Ansatzes bei der Berechnung dieser Eigenschaften für verschiedene radikalische Systeme untersucht. Des Weiteren können mit Hilfe der ersten und zweiten Ableitungen vibronische Kopplungsparameter berechnet werden, welche zur Simulation von Molekülspektren in Kombination mit dem Köppel-Domcke-Cederbaum (KDC)-Modell - in der Arbeit am Beispiel des Formyloxyl (HCO2)-Radikals demonstriert - benötigt werden.rnrnDer konzeptionell einfache EOMIP-CC-Ansatz wurde gewählt, da hier die Wellenfunktion eines Radikalsystems ausgehend von einem stabilen geschlossenschaligen Zustand durch die Entfernung eines Elektrons gebildet wird und somit die Problematik der Symmetriebrechung umgangen werden kann. Im Rahmen der Implementierung wurden neue Programmteile zur Lösung der erforderlichen Gleichungen für die gestörten EOMIP-CC-Amplituden und die gestörten Lagrange-Multiplikatoren zeta zum Quantenchemieprogramm CFOUR hinzugefügt. Die unter Verwendung des Programms bestimmten Eigenschaften werden hinsichtlich ihrer Leistungsfähigkeit im Vergleich zu etablierten Methoden wie z.B. CCSD(T) untersucht. Bei der Berechnung von Polarisierbarkeiten und harmonischen Schwingungsfrequenzen liefert die EOMIP-CCSD-Theorie meist gute Resultate, welche nur wenig von den CCSD(T)-Ergebnissen abweichen. Einzig bei der Betrachtung von Radikalen, für die die entsprechenden Anionen nicht stabil sind (z.B. NH2⁻ und CH3⁻), liefert der EOMIP-CCSD-Ansatz aufgrund methodischer Nachteile keine aussagekräftige Beschreibung. rnrnDie Ableitungen der EOMIP-CCSD-Energie lassen sich auch zur Simulation vibronischer Kopplungen innerhalb des KDC-Modells einsetzen.rnZur Kopplung verschiedener radikalischer Zustände in einem solchen Modellpotential spielen vor allem die Ableitungen von Übergangsmatrixelementen eine wichtige Rolle. Diese sogenannten Kopplungskonstanten können in der EOMIP-CC-Theorie besonders leicht definiert und berechnet werden. Bei der Betrachtung des Photoelektronenspektrums von HCO2⁻ werden zwei Alternativen untersucht: Die vertikale Bestimmung an der Gleichgewichtsgeometrie des HCO2⁻-Anions und die Ermittlung adiabatischer Kraftkonstanten an den Gleichgewichtsgeometrien des Radikals. Lediglich das adiabatische Modell liefert bei Beschränkung auf harmonische Kraftkonstanten eine qualitativ sinnvolle Beschreibung des Spektrums. Erweitert man beide Modelle um kubische und quartische Kraftkonstanten, so nähern sich diese einander an und ermöglichen eine vollständige Zuordnung des gemessenen Spektrums innerhalb der ersten 1500 cm⁻¹. Die adiabatische Darstellung erreicht dabei nahezu quantitative Genauigkeit.

Progetto e sviluppo di un banco prova per articolazioni protesiche attive ad un grado di libertà basato su programmable automation controller e motion capture

L'elaborato descrive il lavoro svolto in cinque mesi presso il Centro Protesi INAIL di Budrio (BO), che ha portato allo sviluppo di un banco prova per testare articolazioni elettromeccaniche. I dispositivi target, in particolare, sono stati due gomiti mioelettrici: il primo di produzione interna INAIL e il secondo prodotto da Selex ES in collaborazione con il Centro Protesi stesso. Per il controllo del movimento e l'acquisizione dei segnali elettrici si è scelto il PAC CompactRIO (National Instruments), mentre per le acquisizioni cinematiche di angolo e velocità angolare si è sfruttata la stereofotogrammetria.

Ottimizzazione di un'unita di controllo per protesi mioelettrica di arto superiore e confronto prestazionale tramite programmable automation controller e motion capture

Con il passare degli anni le tecnologie nel campo delle protesi mioelettriche di arto superiore stanno compiendo sempre più passi in avanti. In questo elaborato di tesi si darà un iniziale introduzione sulla protesica di arto superiore cercando di coprire tutte le possibili tipologie di protesi, prestando particolare attenzione agli arti artificiali mioelettrici. Gli scopi di questo studio sono in prima analisi una miglioria dell'unità di controllo di una protesi comandata da segnali elettromiografici di superficie, tramite l'utilizzo del nuovo IDE della Microchip (MPLAB X). In seconda analisi, invece, si attuerà un confronto prestazionale a livello di consumo in corrente di un prototipo di protesi mioelettrica nata dalla sinergia tra l'azienda "Selex ES" e il "Centro Protesi INAIL di Vigorso di Budrio". Per questo studio ci si è serviti di stereofotogrammetrica per la determinazione delle grandezze meccaniche, mentre tramite un sistema PAC si è riusciti ad ottenere specifiche grandezze elettriche. Lo studio ha portato, a livello di Firmware, l'inserimento del giusto comando di attuazione di un servofreno comandato in corrente e l'introduzione di una particolare modalità a basso consumo che consente un risparmio energetico di circa il 60% rispetto alla vecchia modalità. Discorso diverso per i risultati del confronto prestazionale che non ha portato ai risultati sperati in fase di progetto.

Surface-acoustic-wave counterflow micropumps for on-chip liquid motion control in two-dimensional microchannel arrays

Fully controlled liquid injection and flow in hydrophobic polydimethylsiloxane (PDMS) two-dimensional microchannel arrays based on on-chip integrated, low-voltage-driven micropumps are demonstrated. Our architecture exploits the surface-acoustic-wave (SAW) induced counterflow mechanism and the effect of nebulization anisotropies at crossing areas owing to lateral propagating SAWs. We show that by selectively exciting single or multiple SAWs, fluids can be drawn from their reservoirs and moved towards selected positions of a microchannel grid. Splitting of the main liquid flow is also demonstrated by exploiting multiple SAW beams. As a demonstrator, we show simultaneous filling of two orthogonal microchannels. The present results show that SAW micropumps are good candidates for truly integrated on-chip fluidic networks allowing liquid control in arbitrarily shaped two-dimensional microchannel arrays.

Combining 3D tracking and surgical instrumentation to determine the stiffness of spinal motion segments: a validation study

The spine is a complex structure that provides motion in three directions: flexion and extension, lateral bending and axial rotation. So far, the investigation of the mechanical and kinematic behavior of the basic unit of the spine, a motion segment, is predominantly a domain of in vitro experiments on spinal loading simulators. Most existing approaches to measure spinal stiffness intraoperatively in an in vivo environment use a distractor. However, these concepts usually assume a planar loading and motion. The objective of our study was to develop and validate an apparatus, that allows to perform intraoperative in vivo measurements to determine both the applied force and the resulting motion in three dimensional space. The proposed setup combines force measurement with an instrumented distractor and motion tracking with an optoelectronic system. As the orientation of the applied force and the three dimensional motion is known, not only force-displacement, but also moment-angle relations could be determined. The validation was performed using three cadaveric lumbar ovine spines. The lateral bending stiffness of two motion segments per specimen was determined with the proposed concept and compared with the stiffness acquired on a spinal loading simulator which was considered to be gold standard. The mean values of the stiffness computed with the proposed concept were within a range of ±15% compared to data obtained with the spinal loading simulator under applied loads of less than 5 Nm.

Memory biases in left vs. right implied motion

People remember moving objects as having moved farther along in their path of motion than is actually the case; this is known as representational momentum (RM). Some authors have argued that RM is an internalization of environmental properties such as physical momentum and gravity. Five experiments demonstrated that a similar memory bias could not have been learned from the environment. For right-handed Ss, objects apparently moving to the right engendered a larger memory bias in the direction of motion than did those moving to the left. This effect, clearly not derived from real-world lateral asymmetries, was relatively insensitive to changes in apparent velocity and the type of object used, and it may be confined to objects in the left half of visual space. The left–right effect may be an intrinsic property of the visual operating system, which may in turn have affected certain cultural conventions of left and right in art and other domains.

Dose modulated retrospective ECG-gated versus non-gated 64-row CT angiography of the aorta at the same radiation dose: Comparison of motion artifacts, diagnostic confidence and signal-to-noise-ratios

To compare ECG-gated and non-gated CT angiography of the aorta at the same radiation dose, with regard to motion artifacts (MA), diagnostic confidence (DC) and signal-to-noise-ratios (SNRs).

Biaxial extensional motion of an inertially driven radially expanding liquid sheet

We consider the inertially driven, time-dependent biaxial extensional motion of inviscid and viscous thinning liquid sheets. We present an analytic solution describing the base flow and examine its linear stability to varicose (symmetric) perturbations within the framework of a long-wave model where transient growth and long-time asymptotic stability are considered. The stability of the system is characterized in terms of the perturbation wavenumber, Weber number, and Reynolds number. We find that the isotropic nature of the base flow yields stability results that are identical for axisymmetric and general two-dimensional perturbations. Transient growth of short-wave perturbations at early to moderate times can have significant and lasting influence on the long-time sheet thickness. For finite Reynolds numbers, a radially expanding sheet is weakly unstable with bounded growth of all perturbations, whereas in the inviscid and Stokes flow limits sheets are unstable to perturbations in the short-wave limit.

Interhemispheric connections shape subjective experience of bistable motion

The right and left visual hemifields are represented in different cerebral hemispheres and are bound together by connections through the corpus callosum. Much has been learned on the functions of these connections from split-brain patients [1-4], but little is known about their contribution to conscious visual perception in healthy humans. We used diffusion tensor imaging and functional magnetic resonance imaging to investigate which callosal connections contribute to the subjective experience of a visual motion stimulus that requires interhemispheric integration. The "motion quartet" is an ambiguous version of apparent motion that leads to perceptions of either horizontal or vertical motion [5]. Interestingly, observers are more likely to perceive vertical than horizontal motion when the stimulus is presented centrally in the visual field [6]. This asymmetry has been attributed to the fact that, with central fixation, perception of horizontal motion requires integration across hemispheres whereas perception of vertical motion requires only intrahemispheric processing [7]. We are able to show that the microstructure of individually tracked callosal segments connecting motion-sensitive areas of the human MT/V5 complex (hMT/V5+; [8]) can predict the conscious perception of observers. Neither connections between primary visual cortex (V1) nor other surrounding callosal regions exhibit a similar relationship.