Redox-Switching in a Viologen-type Adlayer: An Electrochemical Shell-Isolated Nanoparticle Enhanced Raman Spectroscopy Study on Au(111)-(1 x 1) Single Crystal Electrodes

We reported the first application of in situ shell-isolated nanoparticle enhanced Raman spectroscopy (SHINERS) to an interfacial redox reaction under electrochemical conditions. We construct gap-mode sandwich structures composed of a thiol-terminated HS-6V6H viologen adlayer immobilized on a single crystal Au(111)-(1x1) electrode and covered by Au(60 nm)@SlO(2) core shell nanoparticles acting as plasmonic antennas. We observed high-quality, potential-dependent Raman spectra of the three viologen species V(2+),V(+center dot) and V(0) on a well-defined Au(111) substrate surface and could map their potential-dependent evolution. Comparison with experiments on powder samples revealed an enhancement factor of the nonresonant Raman modes of similar to 3 x 10(5), and up to 9 x 10(7) for the resonance modes. The study illustrates the unique capability of SHINERS and its potential in the entire field of electrochemical surface science to explore structures and reaction pathways on well-defined substrate surfaces, such as single crystals, for molecular, (electro-)- catalytic, bioelectrochemical systems up to fundamental double layer studies at electrified solid/liquid interfaces.

Geophysical Investigation of Subsurface Three-Dimensional Architecture of Icy Debris Fans With Ground Penetrating Radar in the Wrangell Mountains, Alaska

Icy debris fans have are newly-described landforms (Kochel and Trop, 2008 and 2012) as landforms developed immediately after deglaciation on Earth and similar features have been observed on Mars. Subsurface characteristics of Icy debris fans have not been previously investigated. Ground penetrating radar (GPR) was used to non-invasively investigate the subsurface characteristics of icy debris fans near McCarthy, Alaska, USA. The three fans investigated in Alaska are the East, West, and Middle fans (Kochel and Trop, 2008 and 2012) which below the Nabesna ice cap and on top of the McCarthy Creek Glacier. Icy debris fans in general are a largely unexplored suite of paraglacial landforms and processes in alpine regions. Recent field studies focused on direct observations and depositional processes. Their results showed that the fan's composition is primarily influenced by the type and frequency of depositional processes that supply the fan. Photographic studies show that the East Fan receives far more ice and snow avalanches whereas the Middle and West Fans receive fewer mass wasting events but more clastic debris is deposited on the Middle and West fan from rock falls and icy debris flows. GPR profiles and Wide-angle reflection and refraction (WARR) surveys consisting of both, common mid-point (CMP), and common shot-point (CSP) surveys investigated the subsurface geometry of the fans and the McCarthy Creek Glacier. All GPR surveys were collected in July of 2013 with 100MHz bi-static antennas. Four axial profiles and three cross-fan profiles were done on the West and Middle fans as well as the McCarthy Creek Glacier in order to investigate the relationship between the three features. GPR profiles yielded reflectors that were continuous for 10+ m and hyperbolic reflections in the subsurface. The depth to these reflections in the subsurface requires knowledge of the velocity of the subsurface. To find the velocity of the subsurface eight WARR surveys collected on the fans and on the McCarthy Creek glacier to provide information on variability of subsurface velocities. The profiles of the Middle and West fan have more reflections in their profiles compared to profiles done on the McCarthy Creek Glacier. Based on the WARR surveys, we interpret the lower energy return in the glacier to be caused by two reasons. 1) The increased attenuation due to wet ice versus drier ice and on the fan with GPR velocities >0.15m/ns. 2) Lack of interfaces in the glacier compared to those in the fans which are inferred to be produced by the alternating layers of stratified ice and lithic-rich layers. The GPR profiles on the West and Middle Fans show the shallow subsurface being dominated by lenticular reflections interpreted to be consistent with the shape of surficial deposits. The West Fan is distinguished from the Middle Fan by the nature of its reflections patterns and thicknesses of reflection packages that clearly shows the Middle fan with a greater thickness. The changes in subsurface reflections between the Middle and West Fans as well as the McCarthy Creek Glacier are thought to reflect the type and frequency of depositional processes and surrounding bedrock and talus slopes.

Design Simulation for Solar Energy Research and Education

Solar research is primarily conducted in regions with consistent sunlight, severely limiting research opportunities in many areas. Unfortunately, the unreliable weather in Lewisburg, PA, can prove difficult for such testing to be conducted. As such, a solar simulator was developed for educational purposes for the Mechanical Engineering department at Bucknell University. The objective of this work was to first develop a geometric model to evaluate a one sun solar simulator. This was intended to provide a simplified model that could be used without the necessity of expensive software. This model was originally intended to be validated experimentally, but instead was done using a proven ray tracing program, TracePro. Analyses with the geometrical model and TracePro demonstrated the influence the geometrical properties had results, specifically the reflector (aperture) diameter and the rim angle. Subsequently, the two were approaches were consistent with one another for aperture diameters 0.5 m and larger, and for rim angles larger than 45°. The constructed prototype, that is currently untested, was designed from information provided by the geometric model, includes a metal halide lamp with a 9.5 mm arc diameter and parabolic reflector with an aperture diameter of 0.631 meters. The maximum angular divergence from the geometrical model was predicted to be 30 mRadians. The average angular divergence in TraceProof the system was 19.5 mRadians, compared to the sun’s divergence of 9.2 mRadians. Flux mapping in TracePro showed an intensity of 1000 W/m2 over the target plane located 40 meters from the lamp. The error between spectrum of the metal halide lamp and the solar spectrum was 10.9%, which was found by comparing their respective Plank radiation distributions. The project did not satisfy the original goal of matching the angular divergence of sunlight, although the system could still to be used for optical testing. The geometric model indicated performance in this area could be improved by increasing the diameter of the reflector, as well as decreasing the source diameter. Although ray tracing software provides more information to analyze the simulator system, the geometrical model is adequate to provide enough information to design a system.

An Instrument Design for Space-Based Optical Observation of Space Debris

Currently, observations of space debris are primarily performed with ground-based sensors. These sensors have a detection limit at some centimetres diameter for objects in Low Earth Orbit (LEO) and at about two decimetres diameter for objects in Geostationary Orbit (GEO). The few space-based debris observations stem mainly from in-situ measurements and from the analysis of returned spacecraft surfaces. Both provide information about mostly sub-millimetre-sized debris particles. As a consequence the population of centimetre- and millimetre-sized debris objects remains poorly understood. The development, validation and improvement of debris reference models drive the need for measurements covering the whole diameter range. In 2003 the European Space Agency (ESA) initiated a study entitled “Space-Based Optical Observation of Space Debris”. The first tasks of the study were to define user requirements and to develop an observation strategy for a space-based instrument capable of observing uncatalogued millimetre-sized debris objects. Only passive optical observations were considered, focussing on mission concepts for the LEO, and GEO regions respectively. Starting from the requirements and the observation strategy, an instrument system architecture and an associated operations concept have been elaborated. The instrument system architecture covers the telescope, camera and onboard processing electronics. The proposed telescope is a folded Schmidt design, characterised by a 20 cm aperture and a large field of view of 6°. The camera design is based on the use of either a frame-transfer charge coupled device (CCD), or on a cooled hybrid sensor with fast read-out. A four megapixel sensor is foreseen. For the onboard processing, a scalable architecture has been selected. Performance simulations have been executed for the system as designed, focussing on the orbit determination of observed debris particles, and on the analysis of the object detection algorithms. In this paper we present some of the main results of the study. A short overview of the user requirements and observation strategy is given. The architectural design of the instrument is discussed, and the main tradeoffs are outlined. An insight into the results of the performance simulations is provided.

Study of and design procedure for dual circularly polarized waveguide slot arrays

For the past sixty years, waveguide slot radiator arrays have played a critical role in microwave radar and communication systems. They feature a well-characterized antenna element capable of direct integration into a low-loss feed structure with highly developed and inexpensive manufacturing processes. Waveguide slot radiators comprise some of the highest performance—in terms of side-lobe-level, efficiency, etc. — antenna arrays ever constructed. A wealth of information is available in the open literature regarding design procedures for linearly polarized waveguide slots. By contrast, despite their presence in some of the earliest published reports, little has been presented to date on array designs for circularly polarized (CP) waveguide slots. Moreover, that which has been presented features a classic traveling wave, efficiency-reducing beam tilt. This work proposes a unique CP waveguide slot architecture which mitigates these problems and a thorough design procedure employing widely available, modern computational tools. The proposed array topology features simultaneous dual-CP operation with grating-lobe-free, broadside radiation, high aperture efficiency, and good return loss. A traditional X-Slot CP element is employed with the inclusion of a slow wave structure passive phase shifter to ensure broadside radiation without the need for performance-limiting dielectric loading. It is anticipated this technology will be advantageous for upcoming polarimetric radar and Ka-band SatCom systems. The presented design methodology represents a philosophical shift away from traditional waveguide slot radiator design practices. Rather than providing design curves and/or analytical expressions for equivalent circuit models, simple first-order design rules – generated via parametric studies — are presented with the understanding that device optimization and design will be carried out computationally. A unit-cell, S-parameter based approach provides a sufficient reduction of complexity to permit efficient, accurate device design with attention to realistic, application-specific mechanical tolerances. A transparent, start-to-finish example of the design procedure for a linear sub-array at X-Band is presented. Both unit cell and array performance is calculated via finite element method simulations. Results are confirmed via good agreement with finite difference, time domain calculations. Array performance exhibiting grating-lobe-free, broadside-scanned, dual-CP radiation with better than 20 dB return loss and over 75% aperture efficiency is presented.

Fading pdf of free-space optical communication system with pointing error

A free-space optical (FSO) laser communication system with perfect fast-tracking experiences random power fading due to atmospheric turbulence. For a FSO communication system without fast-tracking or with imperfect fast-tracking, the fading probability density function (pdf) is also affected by the pointing error. In this thesis, the overall fading pdfs of FSO communication system with pointing errors are calculated using an analytical method based on the fast-tracked on-axis and off-axis fading pdfs and the fast-tracked beam profile of a turbulence channel. The overall fading pdf is firstly studied for the FSO communication system with collimated laser beam. Large-scale numerical wave-optics simulations are performed to verify the analytically calculated fading pdf with collimated beam under various turbulence channels and pointing errors. The calculated overall fading pdfs are almost identical to the directly simulated fading pdfs. The calculated overall fading pdfs are also compared with the gamma-gamma (GG) and the log-normal (LN) fading pdf models. They fit better than both the GG and LN fading pdf models under different receiver aperture sizes in all the studied cases. Further, the analytical method is expanded to the FSO communication system with beam diverging angle case. It is shown that the gamma pdf model is still valid for the fast-tracked on-axis and off-axis fading pdfs with point-like receiver aperture when the laser beam is propagated with beam diverging angle. Large-scale numerical wave-optics simulations prove that the analytically calculated fading pdfs perfectly fit the overall fading pdfs for both focused and diverged beam cases. The influence of the fast-tracked on-axis and off-axis fading pdfs, the fast-tracked beam profile, and the pointing error on the overall fading pdf is also discussed. At last, the analytical method is compared with the previous heuristic fading pdf models proposed since 1970s. Although some of previously proposed fading pdf models provide close fit to the experiment and simulation data, these close fits only exist under particular conditions. Only analytical method shows accurate fit to the directly simulated fading pdfs under different turbulence strength, propagation distances, receiver aperture sizes and pointing errors.

Multi-node TOA-DOA cooperative LOS-NLOS localization : enabling high accuracy and reliability

This dissertation investigates high performance cooperative localization in wireless environments based on multi-node time-of-arrival (TOA) and direction-of-arrival (DOA) estimations in line-of-sight (LOS) and non-LOS (NLOS) scenarios. Here, two categories of nodes are assumed: base nodes (BNs) and target nodes (TNs). BNs are equipped with antenna arrays and capable of estimating TOA (range) and DOA (angle). TNs are equipped with Omni-directional antennas and communicate with BNs to allow BNs to localize TNs; thus, the proposed localization is maintained by BNs and TNs cooperation. First, a LOS localization method is proposed, which is based on semi-distributed multi-node TOA-DOA fusion. The proposed technique is applicable to mobile ad-hoc networks (MANETs). We assume LOS is available between BNs and TNs. One BN is selected as the reference BN, and other nodes are localized in the coordinates of the reference BN. Each BN can localize TNs located in its coverage area independently. In addition, a TN might be localized by multiple BNs. High performance localization is attainable via multi-node TOA-DOA fusion. The complexity of the semi-distributed multi-node TOA-DOA fusion is low because the total computational load is distributed across all BNs. To evaluate the localization accuracy of the proposed method, we compare the proposed method with global positioning system (GPS) aided TOA (DOA) fusion, which are applicable to MANETs. The comparison criterion is the localization circular error probability (CEP). The results confirm that the proposed method is suitable for moderate scale MANETs, while GPS-aided TOA fusion is suitable for large scale MANETs. Usually, TOA and DOA of TNs are periodically estimated by BNs. Thus, Kalman filter (KF) is integrated with multi-node TOA-DOA fusion to further improve its performance. The integration of KF and multi-node TOA-DOA fusion is compared with extended-KF (EKF) when it is applied to multiple TOA-DOA estimations made by multiple BNs. The comparison depicts that it is stable (no divergence takes place) and its accuracy is slightly lower than that of the EKF, if the EKF converges. However, the EKF may diverge while the integration of KF and multi-node TOA-DOA fusion does not; thus, the reliability of the proposed method is higher. In addition, the computational complexity of the integration of KF and multi-node TOA-DOA fusion is much lower than that of EKF. In wireless environments, LOS might be obstructed. This degrades the localization reliability. Antenna arrays installed at each BN is incorporated to allow each BN to identify NLOS scenarios independently. Here, a single BN measures the phase difference across two antenna elements using a synchronized bi-receiver system, and maps it into wireless channel’s K-factor. The larger K is, the more likely the channel would be a LOS one. Next, the K-factor is incorporated to identify NLOS scenarios. The performance of this system is characterized in terms of probability of LOS and NLOS identification. The latency of the method is small. Finally, a multi-node NLOS identification and localization method is proposed to improve localization reliability. In this case, multiple BNs engage in the process of NLOS identification, shared reflectors determination and localization, and NLOS TN localization. In NLOS scenarios, when there are three or more shared reflectors, those reflectors are localized via DOA fusion, and then a TN is localized via TOA fusion based on the localization of shared reflectors.

Multi-antenna non-line-of-sight identification techniques for target localization in mobile ad-hoc networks

Target localization has a wide range of military and civilian applications in wireless mobile networks. Examples include battle-field surveillance, emergency 911 (E911), traffc alert, habitat monitoring, resource allocation, routing, and disaster mitigation. Basic localization techniques include time-of-arrival (TOA), direction-of-arrival (DOA) and received-signal strength (RSS) estimation. Techniques that are proposed based on TOA and DOA are very sensitive to the availability of Line-of-sight (LOS) which is the direct path between the transmitter and the receiver. If LOS is not available, TOA and DOA estimation errors create a large localization error. In order to reduce NLOS localization error, NLOS identifcation, mitigation, and localization techniques have been proposed. This research investigates NLOS identifcation for multiple antennas radio systems. The techniques proposed in the literature mainly use one antenna element to enable NLOS identifcation. When a single antenna is utilized, limited features of the wireless channel can be exploited to identify NLOS situations. However, in DOA-based wireless localization systems, multiple antenna elements are available. In addition, multiple antenna technology has been adopted in many widely used wireless systems such as wireless LAN 802.11n and WiMAX 802.16e which are good candidates for localization based services. In this work, the potential of spatial channel information for high performance NLOS identifcation is investigated. Considering narrowband multiple antenna wireless systems, two xvNLOS identifcation techniques are proposed. Here, the implementation of spatial correlation of channel coeffcients across antenna elements as a metric for NLOS identifcation is proposed. In order to obtain the spatial correlation, a new multi-input multi-output (MIMO) channel model based on rough surface theory is proposed. This model can be used to compute the spatial correlation between the antenna pair separated by any distance. In addition, a new NLOS identifcation technique that exploits the statistics of phase difference across two antenna elements is proposed. This technique assumes the phases received across two antenna elements are uncorrelated. This assumption is validated based on the well-known circular and elliptic scattering models. Next, it is proved that the channel Rician K-factor is a function of the phase difference variance. Exploiting Rician K-factor, techniques to identify NLOS scenarios are proposed. Considering wideband multiple antenna wireless systems which use MIMO-orthogonal frequency division multiplexing (OFDM) signaling, space-time-frequency channel correlation is exploited to attain NLOS identifcation in time-varying, frequency-selective and spaceselective radio channels. Novel NLOS identi?cation measures based on space, time and frequency channel correlation are proposed and their performances are evaluated. These measures represent a better NLOS identifcation performance compared to those that only use space, time or frequency.

Utilizing Gaussian-Schell model beams to mitigate atmospheric turbulence in free space optical communications / by Kyle R. Drexler.

Turbulence affects traditional free space optical communication by causing speckle to appear in the received beam profile. This occurs due to changes in the refractive index of the atmosphere that are caused by fluctuations in temperature and pressure, resulting in an inhomogeneous medium. The Gaussian-Schell model of partial coherence has been suggested as a means of mitigating these atmospheric inhomogeneities on the transmission side. This dissertation analyzed the Gaussian-Schell model of partial coherence by verifying the Gaussian-Schell model in the far-field, investigated the number of independent phase control screens necessary to approach the ideal Gaussian-Schell model, and showed experimentally that the Gaussian-Schell model of partial coherence is achievable in the far-field using a liquid crystal spatial light modulator. A method for optimizing the statistical properties of the Gaussian-Schell model was developed to maximize the coherence of the field while ensuring that it does not exhibit the same statistics as a fully coherent source. Finally a technique to estimate the minimum spatial resolution necessary in a spatial light modulator was developed to effectively propagate the Gaussian-Schell model through a range of atmospheric turbulence strengths. This work showed that regardless of turbulence strength or receiver aperture, transmitting the Gaussian-Schell model of partial coherence instead of a fully coherent source will yield a reduction in the intensity fluctuations of the received field. By measuring the variance of the intensity fluctuations and the received mean, it is shown through the scintillation index that using the Gaussian-Schell model of partial coherence is a simple and straight forward method to mitigate atmospheric turbulence instead of traditional adaptive optics in free space optical communications.

Statistics of the received power for free space optical channels

Free space optical (FSO) communication links can experience extreme signal degradation due to atmospheric turbulence induced spatial and temporal irradiance fuctuations (scintillation) in the laser wavefront. In addition, turbulence can cause the laser beam centroid to wander resulting in power fading, and sometimes complete loss of the signal. Spreading of the laser beam and jitter are also artifacts of atmospheric turbulence. To accurately predict the signal fading that occurs in a laser communication system and to get a true picture of how this affects crucial performance parameters like bit error rate (BER) it is important to analyze the probability density function (PDF) of the integrated irradiance fuctuations at the receiver. In addition, it is desirable to find a theoretical distribution that accurately models these ?uctuations under all propagation conditions. The PDF of integrated irradiance fuctuations is calculated from numerical wave-optic simulations of a laser after propagating through atmospheric turbulence to investigate the evolution of the distribution as the aperture diameter is increased. The simulation data distribution is compared to theoretical gamma-gamma and lognormal PDF models under a variety of scintillation regimes from weak to very strong. Our results show that the gamma-gamma PDF provides a good fit to the simulated data distribution for all aperture sizes studied from weak through moderate scintillation. In strong scintillation, the gamma-gamma PDF is a better fit to the distribution for point-like apertures and the lognormal PDF is a better fit for apertures the size of the atmospheric spatial coherence radius ρ0 or larger. In addition, the PDF of received power from a Gaussian laser beam, which has been adaptively compensated at the transmitter before propagation to the receiver of a FSO link in the moderate scintillation regime is investigated. The complexity of the adaptive optics (AO) system is increased in order to investigate the changes in the distribution of the received power and how this affects the BER. For the 10 km link, due to the non-reciprocal nature of the propagation path the optimal beam to transmit is unknown. These results show that a low-order level of complexity in the AO provides a better estimate for the optimal beam to transmit than a higher order for non-reciprocal paths. For the 20 km link distance it was found that, although minimal, all AO complexity levels provided an equivalent improvement in BER and that no AO complexity provided the correction needed for the optimal beam to transmit. Finally, the temporal power spectral density of received power from a FSO communication link is investigated. Simulated and experimental results for the coherence time calculated from the temporal correlation function are presented. Results for both simulation and experimental data show that the coherence time increases as the receiving aperture diameter increases. For finite apertures the coherence time increases as the communication link distance is increased. We conjecture that this is due to the increasing speckle size within the pupil plane of the receiving aperture for an increasing link distance.

Optimal beam forming for laser beam propagation through random media

Focusing optical beams on a target through random propagation media is very important in many applications such as free space optical communica- tions and laser weapons. Random media effects such as beam spread and scintillation can degrade the optical system's performance severely. Compensation schemes are needed in these applications to overcome these random media effcts. In this research, we investigated the optimal beams for two different optimization criteria: one is to maximize the concentrated received intensity and the other is to minimize the scintillation index at the target plane. In the study of the optimal beam to maximize the weighted integrated intensity, we derive a similarity relationship between pupil-plane phase screen and extended Huygens-Fresnel model, and demonstrate the limited utility of maximizing the average integrated intensity. In the study ofthe optimal beam to minimize the scintillation index, we derive the first- and second-order moments for the integrated intensity of multiple coherent modes. Hermite-Gaussian and Laguerre-Gaussian modes are used as the coherent modes to synthesize an optimal partially coherent beam. The optimal beams demonstrate evident reduction of scintillation index, and prove to be insensitive to the aperture averaging effect.

DIFFERENTIATING PATH AND SOURCE PROCESSES IN COMPLEX GEOLOGIC STRUCTURE THROUGH PASSIVE SEISMIC STUDIES: BERING GLACIER, ALASKA AND VILLARRICA VOLCANO, CHILE

Measuring shallow seismic sources provides a way to reveal processes that cannot be directly observed, but the correct interpretation and value of these signals depend on the ability to distinguish source from propagation effects. Furthermore, seismic signals produced by a resonating source can look almost identical to those produced by impulsive sources, but modified along the path. Distinguishing these two phenomena can be accomplished by examining the wavefield with small aperture arrays or by recording seismicity near to the source when possible. We examine source and path effects in two different environments: Bering Glacier, Alaska and Villarrica Volcano, Chile. Using three 3-element seismic arrays near the terminus of the Bering Glacier, we have identified and located both terminus calving and iceberg breakup events. We show that automated array analysis provided a robust way to locate icequake events using P waves. This analysis also showed that arrivals within the long-period codas were incoherent within the small aperture arrays, demonstrating that these codas previously attributed to crack resonance were in fact a result of a complicated path rather than a source effect. At Villarrica Volcano, seismometers deployed from near the vent to ~10 km revealed that a several cycle long-period source signal recorded at the vent appeared elongated in the far-field. We used data collected from the stations nearest to the vent to invert for the repetitive seismic source, and found it corresponded to a shallow force within the lava lake oriented N75°E and dipping 7° from horizontal. We also used this repetitive signal to search the data for additional seismic and infrasonic properties which included calculating seismic-acoustic delay times, volcano acoustic-seismic ratios and energies, event frequency, and real-time seismic amplitude measurements. These calculations revealed lava lake level and activity fluctuations consistent with lava lake level changes inferred from the persistent infrasonic tremor.