Quantum transport in a single molecular junction

The craze for faster and smaller electronic devices has never gone down and this has always kept researchers on their toes. Following Moore’s law, which states that the number of transistors in a single chip will double in every 18 months, today “30 million transistors can fit into the head of a 1.5 mm diameter pin”. But this miniaturization cannot continue indefinitely due to the ‘quantum leakage’ limit in the thickness of the insulating layer between the gate electrode and the current carrying channel. To bypass this limitation, scientists came up with the idea of using vastly available organic molecules as components in an electronic device. One of the primary challenges in this field was the ability to perform conductance measurements across single molecular junctions. Once that was achieved the focus shifted to a deeper understanding of the underlying physics behind the electron transport across these molecular scale devices. Our initial theoretical approach is based on the conventional Non-Equilibrium Green Function(NEGF) formulation, but the self-energy of the leads is modified to include a weighting factor that ensures negligible current in the absence of a molecular pathway as observed in a Mechanically Controlled Break Junction (MCBJ) experiment. The formulation is then made parameter free by a more careful estimation of the self-energy of the leads. The calculated conductance turns out to be atleast an order more than the experimental values which is probably due to a strong chemical bond at the metal-molecule junction unlike in the experiments. The focus is then shifted to a comparative study of charge transport in molecular wires of different lengths within the same formalism. The molecular wires, composed of a series of organic molecules, are sanwiched between two gold electrodes to make a two terminal device. The length of the wire is increased by sequentially increasing the number of molecules in the wire from 1 to 3. In the low bias regime all the molecular devices are found to exhibit Ohmic behavior. However, the magnitude of conductance decreases exponentially with increase in length of the wire. In the next study, the relative contribution of the ‘in-phase’ and the ‘out-of-phase’ components of the total electronic current under the influence of an external bias is estimated for the wires of three different lengths. In the low bias regime, the ‘out-of-phase’ contribution to the total current is minimal and the ‘in-phase’ elastic tunneling of the electrons is responsible for the net electronic current. This is true irrespective of the length of the molecular spacer. In this regime, the current-voltage characteristics follow Ohm’s law and the conductance of the wires is found to decrease exponentially with increase in length which is in agreement with experimental results. However, after a certain ‘off-set’ voltage, the current increases non-linearly with bias and the ‘out-of-phase’ tunneling of electrons reduces the net current substantially. Subsequently, the interaction of conduction electrons with the vibrational modes as a function of external bias in the three different oligomers is studied since they are one of the main sources of phase-breaking scattering. The number of vibrational modes that couple strongly with the frontier molecular orbitals are found to increase with length of the spacer and the external field. This is consistent with the existence of lowest ‘off-set’ voltage for the longest wire under study.

MIMO waveform design using continuous phase modulation

Hybrid MIMO Phased-Array Radar (HMPAR) is an emerging technology that combines MIMO (multiple-in, multiple-out) radar technology with phased-array radar technology. The new technology is in its infancy, but much of the theoretical work for this specific project has already been completed and is explored in great depth in [1]. A brief overview of phased-array radar systems, MIMO radar systems, and the HMPAR paradigm are explored in this paper. This report is the culmination of an effort to support research in MIMO and HMPAR utilizing a concept called intrapulse beamscan. Using intrapulse beamscan, arbitrary spatial coverage can be achieved within one MIMO beam pulse. Therefore, this report focuses on designing waveforms for MIMO radar systems with arbitrary spatial coverage using that phenomenon. With intrapulse beamscan, scanning is done through phase-modulated signal design within one pulse rather than phase-shifters in the phased array over multiple pulses. In addition to using this idea, continuous phase modulation (CPM) signals are considered for their desirable peak-to-average ratio property as well as their low spectral leakage. These MIMO waveforms are designed with three goals in mind. The first goal is to achieve flexible spatial coverage while utilizing intrapulse beamscan. As with almost any radar system, we wish to have flexibility in where we send our signal energy. The second goal is to maintain a peak-to-average ratio close to 1 on the envelope of these waveforms, ensuring a signal that is close to constant modulus. It is desired to have a radar system transmit at the highest available power; not doing so would further diminish the already very small return signals. The third goal is to ensure low spectral leakage using various techniques to limit the bandwidth of the designed signals. Spectral containment is important to avoid interference with systems that utilize nearby frequencies in the electromagnetic spectrum. These three goals are realized allowing for limitations of real radar systems. In addition to flexible spatial coverage, the report examines the spectral properties of utilizing various space-filling techniques for desired spatial areas. The space-filling techniques examined include Hilbert/Peano curves and standard raster scans.

Synthesis of novel solid materials from carbon dioxide and carbon monoxide

The increase of atmospheric CO2 has been identified as the primary cause for the observed global warming over the past century. The geological and oceanic sequestration of CO2 has issues, such as cost and leakage as well as effects on sea biota. The ideal solution should be the conversion of CO2 into useful materials. However, most processes require high energy input. Therefore, it is necessary to explore novel processes with low energy demands to convert CO2 to useful solid materials. Amorphous carbon nitride and graphone received much attention due to their unusual structures and properties as well as their potential applications. However, to date there has been no attempt to synthesize those solid materials from CO2. Lithium nitride (Li3N) and lithium imide (Li2NH) are important hydrogen storage materials. However, their optical properties and reactivity has not yet studied. This dissertation research is aimed at the synthesis of carbon nitrides and graphone from CO2 and CO via their reaction with Li3N and Li2NH. The research was focused on (1) the evaluation of Li3N and Li2NH properties, (2) thermodynamic analysis of conversion of carbon dioxide and carbon monoxide into carbon nitride and other solid materials, (3) synthesis of carbon nitride from carbon dioxide, and (4) synthesis of graphone from carbon monoxide. First, the properties of Li3N, Li2NH, and LiNH2 were investigated. The X-ray diffraction measurements revealed that heat-treatment at 500°C introduce a phase transformation of β-Li3N to α-Li3N. Furthermore, the UV-visible absorption evaluation showed that the energy gaps of α-Li3N and β-Li3N are 1.81 and 2.14 eV, respectively. The UV-visible absorption measurements also revealed that energy gaps are 3.92 eV for Li2NH and 3.93 eV for LiNH2. This thermodynamic analysis was performed to predict the reactions. It was demonstrated that the reaction between carbon dioxide and lithium nitride is thermodynamically favorable and exothermic, which can generate carbon nitride and lithium cyanamide. Furthermore, the thermodynamic calculation indicated that the reaction between carbon monoxide and lithium imide can produce graphone and lithium cyanamide along with releasing heat. Based on the above thermodynamic analysis, the experiment of CO2 and Li3N reaction and CO and Li2NH were carried out. It was found that the reaction between CO2 and Li3N is very fast and exothermic. The XRD and element analysis revealed that the products are crystal lithium cyanamide and amorphous carbon nitrides with Li2O and Li2CO3. Furthermore, TEM images showed that carbon nitrides possess layer-structure, namely, it is graphene-structured carbon nitride. It was found that the reaction between Li2NH and CO was also exothermic, which produced graphone instead of carbon nitride. The composition and structures of graphone were evaluated by XRD, element analysis, TEM observation, and Raman spectra.

Transformer modeling ATP : internal faults & high-frequency discretization

Power transformers are key components of the power grid and are also one of the most subjected to a variety of power system transients. The failure of a large transformer can cause severe monetary losses to a utility, thus adequate protection schemes are of great importance to avoid transformer damage and maximize the continuity of service. Computer modeling can be used as an efficient tool to improve the reliability of a transformer protective relay application. Unfortunately, transformer models presently available in commercial software lack completeness in the representation of several aspects such as internal winding faults, which is a common cause of transformer failure. It is also important to adequately represent the transformer at frequencies higher than the power frequency for a more accurate simulation of switching transients since these are a well known cause for the unwanted tripping of protective relays. This work develops new capabilities for the Hybrid Transformer Model (XFMR) implemented in ATPDraw to allow the representation of internal winding faults and slow-front transients up to 10 kHz. The new model can be developed using any of two sources of information: 1) test report data and 2) design data. When only test-report data is available, a higher-order leakage inductance matrix is created from standard measurements. If design information is available, a Finite Element Model is created to calculate the leakage parameters for the higher-order model. An analytical model is also implemented as an alternative to FEM modeling. Measurements on 15-kVA 240?/208Y V and 500-kVA 11430Y/235Y V distribution transformers were performed to validate the model. A transformer model that is valid for simulations for frequencies above the power frequency was developed after continuing the division of windings into multiple sections and including a higher-order capacitance matrix. Frequency-scan laboratory measurements were used to benchmark the simulations. Finally, a stability analysis of the higher-order model was made by analyzing the trapezoidal rule for numerical integration as used in ATP. Numerical damping was also added to suppress oscillations locally when discontinuities occurred in the solution. A maximum error magnitude of 7.84% was encountered in the simulated currents for different turn-to-ground and turn-to-turn faults. The FEM approach provided the most accurate means to determine the leakage parameters for the ATP model. The higher-order model was found to reproduce the short-circuit impedance acceptably up to about 10 kHz and the behavior at the first anti-resonant frequency was better matched with the measurements.

TIME LAPSE SEISMIC OBSERVATIONS AND EFFECTS OF RESERVOIR COMPRESSIBILITY AT TEAL SOUTH OIL FIELD

One of the original ocean-bottom time-lapse seismic studies was performed at the Teal South oil field in the Gulf of Mexico during the late 1990’s. This work reexamines some aspects of previous work using modern analysis techniques to provide improved quantitative interpretations. Using three-dimensional volume visualization of legacy data and the two phases of post-production time-lapse data, I provide additional insight into the fluid migration pathways and the pressure communication between different reservoirs, separated by faults. This work supports a conclusion from previous studies that production from one reservoir caused regional pressure decline that in turn resulted in liberation of gas from multiple surrounding unproduced reservoirs. I also provide an explanation for unusual time-lapse changes in amplitude-versus-offset (AVO) data related to the compaction of the producing reservoir which, in turn, changed an isotropic medium to an anisotropic medium. In the first part of this work, I examine regional changes in seismic response due to the production of oil and gas from one reservoir. The previous studies primarily used two post-production ocean-bottom surveys (Phase I and Phase II), and not the legacy streamer data, due to the unavailability of legacy prestack data and very different acquisition parameters. In order to incorporate the legacy data in the present study, all three poststack data sets were cross-equalized and examined using instantaneous amplitude and energy volumes. This approach appears quite effective and helps to suppress changes unrelated to production while emphasizing those large-amplitude changes that are related to production in this noisy (by current standards) suite of data. I examine the multiple data sets first by using the instantaneous amplitude and energy attributes, and then also examine specific apparent time-lapse changes through direct comparisons of seismic traces. In so doing, I identify time-delays that, when corrected for, indicate water encroachment at the base of the producing reservoir. I also identify specific sites of leakage from various unproduced reservoirs, the result of regional pressure blowdown as explained in previous studies; those earlier studies, however, were unable to identify direct evidence of fluid movement. Of particular interest is the identification of one site where oil apparently leaked from one reservoir into a “new” reservoir that did not originally contain oil, but was ideally suited as a trap for fluids leaking from the neighboring spill-point. With continued pressure drop, oil in the new reservoir increased as more oil entered into the reservoir and expanded, liberating gas from solution. Because of the limited volume available for oil and gas in that temporary trap, oil and gas also escaped from it into the surrounding formation. I also note that some of the reservoirs demonstrate time-lapse changes only in the “gas cap” and not in the oil zone, even though gas must be coming out of solution everywhere in the reservoir. This is explained by interplay between pore-fluid modulus reduction by gas saturation decrease and dry-frame modulus increase by frame stiffening. In the second part of this work, I examine various rock-physics models in an attempt to quantitatively account for frame-stiffening that results from reduced pore-fluid pressure in the producing reservoir, searching for a model that would predict the unusual AVO features observed in the time-lapse prestack and stacked data at Teal South. While several rock-physics models are successful at predicting the time-lapse response for initial production, most fail to match the observations for continued production between Phase I and Phase II. Because the reservoir was initially overpressured and unconsolidated, reservoir compaction was likely significant, and is probably accomplished largely by uniaxial strain in the vertical direction; this implies that an anisotropic model may be required. Using Walton’s model for anisotropic unconsolidated sand, I successfully model the time-lapse changes for all phases of production. This observation may be of interest for application to other unconsolidated overpressured reservoirs under production.