Electron spectroscopy of novel charge transfer systems based on polycyclic aromatic hydrocarbons

Organische Ladungstransfersysteme weisen eine Vielfalt von konkurrierenden Wechselwirkungen zwischen Ladungs-, Spin- und Gitterfreiheitsgraden auf. Dies führt zu interessanten physikalischen Eigenschaften, wie metallische Leitfähigkeit, Supraleitung und Magnetismus. Diese Dissertation beschäftigt sich mit der elektronischen Struktur von organischen Ladungstransfersalzen aus drei Material-Familien. Dabei kamen unterschiedliche Photoemissions- und Röntgenspektroskopietechniken zum Einsatz. Die untersuchten Moleküle wurden z.T. im MPI für Polymerforschung synthetisiert. Sie stammen aus der Familie der Coronene (Donor Hexamethoxycoronen HMC und Akzeptor Coronen-hexaon COHON) und Pyrene (Donor Tetra- und Hexamethoxypyren TMP und HMP) im Komplex mit dem klassischen starken Akzeptor Tetracyanoquinodimethan (TCNQ). Als dritte Familie wurden Ladungstransfersalze der k-(BEDT-TTF)2X Familie (X ist ein monovalentes Anion) untersucht. Diese Materialien liegen nahe bei einem Bandbreite-kontrollierten Mottübergang im Phasendiagramm.rnFür Untersuchungen mittels Ultraviolett-Photoelektronenspektroskopie (UPS) wurden UHV-deponierte dünne Filme erzeugt. Dabei kam ein neuer Doppelverdampfer zum Einsatz, welcher speziell für Milligramm-Materialmengen entwickelt wurde. Diese Methode wies im Ladungstransferkomplex im Vergleich mit der reinen Donor- und Akzeptorspezies energetische Verschiebungen von Valenzzuständen im Bereich weniger 100meV nach. Ein wichtiger Aspekt der UPS-Messungen lag im direkten Vergleich mit ab-initio Rechnungen.rnDas Problem der unvermeidbaren Oberflächenverunreinigungen von lösungsgezüchteten 3D-Kristallen wurde durch die Methode Hard-X-ray Photoelectron Spectroscopy (HAXPES) bei Photonenenergien um 6 keV (am Elektronenspeicherring PETRA III in Hamburg) überwunden. Die große mittlere freie Weglänge der Photoelektronen im Bereich von 15 nm resultiert in echter Volumensensitivität. Die ersten HAXPES Experimente an Ladungstransferkomplexen weltweit zeigten große chemische Verschiebungen (mehrere eV). In der Verbindung HMPx-TCNQy ist die N1s-Linie ein Fingerabdruck der Cyanogruppe im TCNQ und zeigt eine Aufspaltung und einen Shift zu höheren Bindungsenergien von bis zu 6 eV mit zunehmendem HMP-Gehalt. Umgekehrt ist die O1s-Linie ein Fingerabdruck der Methoxygruppe in HMP und zeigt eine markante Aufspaltung und eine Verschiebung zu geringeren Bindungsenergien (bis zu etwa 2,5eV chemischer Verschiebung), d.h. eine Größenordnung größer als die im Valenzbereich.rnAls weitere synchrotronstrahlungsbasierte Technik wurde Near-Edge-X-ray-Absorption Fine Structure (NEXAFS) Spektroskopie am Speicherring ANKA Karlsruhe intensiv genutzt. Die mittlere freie Weglänge der niederenergetischen Sekundärelektronen (um 5 nm). Starke Intensitätsvariationen von bestimmten Vorkanten-Resonanzen (als Signatur der unbesetzte Zustandsdichte) zeigen unmittelbar die Änderung der Besetzungszahlen der beteiligten Orbitale in der unmittelbaren Umgebung des angeregten Atoms. Damit war es möglich, präzise die Beteiligung spezifischer Orbitale im Ladungstransfermechanismus nachzuweisen. Im genannten Komplex wird Ladung von den Methoxy-Orbitalen 2e(Pi*) und 6a1(σ*) zu den Cyano-Orbitalen b3g und au(Pi*) und – in geringerem Maße – zum b1g und b2u(σ*) der Cyanogruppe transferiert. Zusätzlich treten kleine energetische Shifts mit unterschiedlichem Vorzeichen für die Donor- und Akzeptor-Resonanzen auf, vergleichbar mit den in UPS beobachteten Shifts.rn

Acetabular reinforcement ring in primary total hip arthroplasty: a minimum 10-year follow-up

INTRODUCTION: We report the results of a titanium acetabular reinforcement ring with a hook (ARRH) in primary total hip arthroplasty (THA), which was introduced in 1987 and continues to be used routinely in our center. The favorable results of this device in arthroplasty for developmental dysplasia and difficult revisions motivated its use in primary THA. With this implant only minimal acetabular reaming is necessary, anatomic positioning is achieved by placing the hook around the teardrop and a homogenous base for cementing the polyethylene cup is provided. MATERIALS AND METHODS: Between April 1987 and December 1991, 241 THAs with insertion of an ARRH were performed in 178 unselected, consecutive patients (average age 58 years; range 30-84 years) with a secondary osteoarthrosis in 41% of the cases. RESULTS: At the time of the latest follow-up, 33 patients (39 hips) had died and 17 cases had been lost to follow-up. The median follow-up was 122 months with a minimum of 10 years. Eight hips had been revised, leaving 177 hips in 120 living patients without revision. Six cups were revised because of aseptic loosening. Two hips were revised for sepsis. The mean Merle d'Aubigné score for the remaining hips was 16 (range 7-18) at the latest follow-up. For aseptic loosening, the probability of survival of the cup was 0.97 (95% confidence interval, 0.94-0.99). However, analysis of radiographs implied loosening in seven other cups without clinical symptoms. CONCLUSIONS: The results of primary THA using an acetabular reinforcement ring parallel the excellent results of these implants often observed in difficult primary and revision arthroplasty at a minimum of 10 years. Survivorship is comparable to modern cementless implants. Medial migration that occurs with loosening of the acetabular component seems to be prevented with this implant. Radiographic loosening signs can exist without clinical symptoms.

SMARTnet: First Experience of Setting Up a Telescope System to Survey the Geostationary Ring

Space debris in geostationary orbits may be detected with optical telescopes when the objects are illuminated by the Sun. The advantage compared to Radar can be found in the illumination: radar illuminates the objects and thus the detection sensitivity depletest proportional to the fourth power of the d istance. The German Space Operation Center, GSOC, together with the Astronomical Institute of the University of Bern, AIUB, are setting up a telescope system called SMARTnet to demonstrate the capability of performing geostationary surveillance. Such a telescope system will consist of two telescopes on one mount: a smaller telescope with an aperture of 20cm will serve for fast survey while the larger one, a telescope with an aperture of 50cm, will be used for follow-up observations. The telescopes will be operated by GSOC from Oberpfaffenhofen by the internal monitoring and control system called SMARTnetMAC. The observation plan will be generated by MARTnetPlanning seven days in advance by applying an optimized planning scheduler, taking into account fault time like cloudy nights, priority of objects etc. From each picture taken, stars will be identified and everything not being a star is treated as a possible object. If the same object can be identified on multiple pictures within a short time span, the trace is called a tracklet. In the next step, several tracklets will be correlated to identify individual objects, ephemeris data for these objects are generated and catalogued . This will allow for services like collision avoidance to ensure safe operations for GSOC’s satellites. The complete data processing chain is handled by BACARDI, the backbone catalogue of relational debris information and is presented as a poster.

Probing the Structure, Pseudorotation, and Radial Vibrations of Cyclopentane by Femtosecond Rotational Raman Coherence Spectroscopy

Femtosecond time-resolved Raman rotational coherence spectroscopy (RCS) is employed to determine accurate rotational, vibration–rotation coupling constants, and centrifugal distortion constants of cyclopentane (C⁵H¹⁰). Its lowest-frequency vibration is a pseudorotating ring deformation that interconverts 10 permutationally distinct but energetically degenerate “twist” minima interspersed by 10 “bent” conformers. While the individual twist and bent structures are polar asymmetric tops, the pseudorotation is fast on the time scale of external rotation, rendering cyclopentane a fluxionally nonpolar symmetric top molecule. The pseudorotational level pattern corresponds to a one-dimensional internal rotor with a pseudorotation constant Bps ≈ 2.8 cm⁻¹. The pseudorotational levels are significantly populated up to l = ± 13 at 298 K; <10% of the molecules are in the l = 0 level. The next-higher vibration is the “radial” ν²³ ring deformation mode at 273 cm⁻¹, which is far above the pseudorotational fundamental. Femtosecond Raman RCS measurements were performed in a gas cell at T = 293 K and in a pulsed supersonic jet at T ≈ 90 K. The jet cooling reduces the pseudorotational distribution to l < ±8 and eliminates the population of ν²³, allowing one to determine the rotational constant as A0 = B0 = 6484.930(11) MHz. This value is ∼300 times more precise than the previous value. The fit of the RCS transients reveals that the rotation–pseudorotation coupling constant αe,psB = −0.00070(1) MHz is diminutive, implying that excitation of the pseudorotation has virtually no effect on the B0 rotational constant of cyclopentane. The smallness of αe,psB can be realized when comparing to the vibration–rotation coupling constant of the ν²³ vibration, αe,23B = −9.547(1) MHz, which is about 10⁴ times larger.

Pulse shaping in mode-locked ring-cavity fibre lasers

By means of extensive numerical modelling we have demonstrated the possibility of nonlinear pulse shaping in a mode-locked fibre laser using control of the intra-cavity propagation dynamics by adjustment of the normal net dispersion and integrated gain. Beside self-similar mode-locking, the existence of a novel type of pulse shaping regime that produces pulses with a triangular temporal intensity profile and a linear frequency chirp has been observed.

Multi-wavelength switchable fibre ring laser based on polarisation selective tilted fibre gratings capable of strain and temperature sensing

Using three fibre gratings with excessively tilted structures in the cavity, we have experimentally demonstrated a multiwavelength switchable erbium-doped fibre ring laser system. The three tilted gratings act as in-fibre polariser and polarisation dependent loss filters to induce the polarisation hole burning effect in the cavity for the operation of the laser at single, double, triple and quadruple wavelengths. The laser system has demonstrated good stability under room temperature conditions and also achieved a high degree of polarization (~30dB), high optical signal to noise ratio (up to 63dB) and high side mode suppression (~50dB). The system has also been investigated for temperature and strain sensing by subjecting the seeding fibre Bragg gratings (FBG) to temperature and strain variations. Since the loss band of the polarisation dependent loss filter is broader than the bandwidth of the seeding FBG, the laser output shifts in wavelength with the applied temperature and strain. The fibre ring laser has shown good responses to the temperature and strain, providing sensitivities of approximately 11.7 pm/°C and 0.85pm/µe respectively.

Pulse shaping in mode-locked ring-cavity fibre lasers

By means of extensive numerical modelling we have demonstrated the possibility of nonlinear pulse shaping in a mode-locked fibre laser using control of the intra-cavity propagation dynamics by adjustment of the normal net dispersion and integrated gain. Beside self-similar mode-locking, the existence of a novel type of pulse shaping regime that produces pulses with a triangular temporal intensity profile and a linear frequency chirp has been observed.

Impact of the order of cavity elements in all-normal dispersion ring fiber lasers

Nonlinearity plays a critical role in the intra-cavity dynamics of high-pulse energy fiber lasers. Management of the intra-cavity nonlinear dynamics is the key to increase the output pulse energy in such laser systems. Here, we examine the impact of the order of the intra-cavity elements on the energy of generated pulses in the all-normal dispersion mode-locked ring fiber laser cavity. In mathematical terms, the nonlinear light dynamics in resonator makes operators corresponding to the action of laser elements (active and passive fiber, out-coupler, saturable absorber) non-commuting and the order of their appearance in a cavity important. For the simple design of all-normal dispersion ring fiber laser with varying cavity length, we found the order of the cavity elements, leading to maximum output pulse energy.

Multi-wavelength switchable fibre ring laser based on polarisation selective tilted fibre gratings capable of strain and temperature sensing

Using three fibre gratings with excessively tilted structures in the cavity, we have experimentally demonstrated a multiwavelength switchable erbium-doped fibre ring laser system. The three tilted gratings act as in-fibre polariser and polarisation dependent loss filters to induce the polarisation hole burning effect in the cavity for the operation of the laser at single, double, triple and quadruple wavelengths. The laser system has demonstrated good stability under room temperature conditions and also achieved a high degree of polarization (~30dB), high optical signal to noise ratio (up to 63dB) and high side mode suppression (~50dB). The system has also been investigated for temperature and strain sensing by subjecting the seeding fibre Bragg gratings (FBG) to temperature and strain variations. Since the loss band of the polarisation dependent loss filter is broader than the bandwidth of the seeding FBG, the laser output shifts in wavelength with the applied temperature and strain. The fibre ring laser has shown good responses to the temperature and strain, providing sensitivities of approximately 11.7 pm/°C and 0.85pm/µe respectively.

Optical loading sensor based on ring-cavity fiber laser incorporating a 45°-tilted fiber polarizing grating

We have experimentally demonstrated an active loading sensor system based on a fiber ring laser with singlepolarization output using an intra-cavity 45°-tilted fiber grating. When the laser cavity fiber is subjected to loading, the laser output is encoded with the loading information that can be measured and monitored by a standard power meter. The achieved loading sensitivity is 0.033/kg • m-1 and 0.042/kg • m-1 for two different interaction lengths. The experimental results clearly show that such a single-polarization fiber laser may be commercially developed into a low-cost, high-sensitivity loading sensor system.

Higher-order soliton generation in hybrid mode-locked thulium-doped fiber ring laser

A thulium-doped all-fiber laser passively mode-locked by the co-action of nonlinear polarization evolution and single-walled carbon nanotubes operating at 1860-1980 nm wavelength band is demonstrated. Pumped with the single-mode laser diode at 1.55 μm laser generates near 500-fs soliton pulses at repetition rate ranging from 6.3 to 72.5 MHz in single-pulse operation regime. Having 3-m long cavity average output power reached 300 mW, giving the peak power of 4.88 kW and the pulse energy of 2.93 nJ with slope efficiency higher than 30%. At a 21.6-m long ring cavity average output power of 117 mW is obtained, corresponding to the pulse energy up to 10.87 nJ and a pulse peak power of 21.7 kW, leading to the higher-order soliton generation.

Polarization switchable single/multi-wavelength fiber ring laser with an intra-cavity all fiber Lyot filter

we demonstrate a polarization switchable, single/ multi-wavelength fiber ring laser based on an intra-cavity all fiber Lyot filter. The laser can operate at single-, multi-wavelength by adjusting polarization controller, and givessingle polarization output. © 2015 OSA.

Dynamics of vector rogue waves in a fiber laser with a ring cavity

A pulse–pulse interaction that leads to rogue wave (RW) generation in lasers was previously attributed either to soliton–soliton or soliton–dispersive-wave interaction. The beating between polarization modes in the absence of a saturable absorber causes similar effects. Accounting for these polarization modes in a laser resonator is the purpose of the distributed vector model of laser resonators. Furthermore, high pump power, high amplitude, and short pulse duration are not necessary conditions to observe pulse attraction, repulsion, and collisions and the resonance exchange of energy between among them. The regimes of interest can be tuned just by changing the birefringence in the cavity with the pump power slightly higher than the laser threshold. This allows the observation of a wide range of RW patterns in the same experiment, as well as to classify them. The dynamics of the interaction between pulses leads us to the conclusion that all of these effects occur due to nonlinearity induced by the inverse population in the active fiber as well as an intrinsic nonlinearity in the passive part of the cavity. Most of the mechanisms of pulse–pulse interaction were found to be mutually exclusive. This means that all the observed RW patterns, namely, the “lonely,” “twins,” “three sisters,” and “cross,” are probably different cases of the same process.