<div>The chemical complexity of hydrocarbon fuels and the fast-expanding list of potential plantderived biofuels pose a challenge to the scientific community seeking to provide a molecular understanding of their combustion. More refined spectroscopic tools and methodologies must be developed to selectively detect and characterize the widening array of fuel components and combustion reactive intermediates. The direct relationship between molecular structure and rotational frequencies makes rotational spectroscopy highly structural specific; therefore, it offers a powerful means of characterizing pyrolysis ntermediates. This thesis describes experimental work using broadband microwave spectroscopy to address a number of challenging problems in the spectroscopy of gas complex mixtures.</div><div><br></div><div>Usually, the observed rotational spectra contain contributions from many distinct species, creating a complicated spectrum with interleaved transitions that make spectral assignment challenging. To assist with the process, a protocol called “strong-field coherence breaking” (SFCB) has been developed. It exploits multi-resonance effects that accompany sweeping the microwave radiation under strong-field conditions to output a set of transitions that can confidently be assigned to a single component in a mixture, thereby reducing the spectral assignment time.</div><div><br></div><div>The broadband chirped pulse Fourier transform microwave (CP-FTMW) spectra of guaiacol, syringol, 4-methyl guaiacol, 4-vinyl guaiacol were recorded under jet- cooled conditions over the 2-18 GHz frequency range. Using data from the 13C isotopomers the r0 structure of guaiacol was determined by means of a Kraitchman analysis. The tunneling due to OH hindered rotation was observed in syringol and the V2 barrier was deduced to be 50% greater than phenol’s barrier. This is due to the intramolecular H-bonding between the hydroxy and the methoxy groups. The internal rotation barrier for the methyl group for 4-methyl guaiacol was also determined. Moreover, the spectral assignment of the two conformers of 4-vinyl guaiacol was sped-up by using SFCB. The main structural insight from these lignin-related molecules was that polar substituents dictate the magnitude and type of structural shift that occurs relative to that of the unsubstituted aromatic ring.</div><div><br></div><div>In the next part of my work, the pyrolysis of 2-methoxy furan was carried out over the 300-1600 K temperature range, with microwave detection in the 2-18 GHz frequency range, using hightemperature flash pyrolysis micro-reactor coupled with a supersonic expansion. The SFCB technique was used to analyze and speed up the line assignment. The 2-furanyloxy radical, a primary, resonance-stabilized radical formed by loss of a methyl group in the pyrolysis of 2-methoxy furan, was detected and its molecular parameters were determined.</div><div><br></div><div>Finally, a unique setup that combines the high-resolution spectroscopic data provided by chirped pulse Fourier transform microwave (CP-FTMW) spectroscopy with photoionization mass spectra from a vacuum ultraviolet (VUV) time-of-flight mass spectrometer (TOF-MS) was used to find optimal conditions to detect reactive intermediates and make full assignments for the microwave spectra of phenoxy radical and o-hydroxy phenoxy radical over the 2-18 GHz range. Phenoxy radical was generated through the pyrolysis of anisole and allyl phenyl ether. Using a combination of data from 13C isotopomers and fully deuterated phenoxy radical, in combination with high level ab initio calculations, a near-complete r0 structure for the radical was obtained. The structural data point to the radical being a primarily carbon-centered rather than oxygencentered radical. Using guaiacol as precursor, we studied the spectroscopy of the o-hydroxy phenoxy radical, whose structural data is compared with that of phenoxy to understand the role played by the hydroxyl group in modifying the resonance stabilization of the radical.</div><div><br></div>

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In recent years, the wireless industry has witnessed tremendous development for the defense and commercial segments. The explosive growth in the modern radio frequency and microwave systems leads to an increased interest in the research of miniaturized microwave circuits with superior performance. Broadband components, in particular band pass filters (BPFs) and couplers are some of the widely used components in the modern communication systems, software defined radios, cognitive radios, imaging systems and positioning radars. In order to meet these requirements, the use of innovative geometries, a thorough understanding of their behavior by appropriate analytical techniques and the use of appropriate fabrication approaches are essential. This thesis is an effort in this direction. In this thesis work, an aperture in the ground plane is used to achieve the tight coupling in the edge and broadside-coupled coupled lines which may be otherwise difficult due to the fabrication limitations. Since microstrip lines with an aperture in the ground plane are found to be very useful in various MIC and MMIC components, closed form analytical expressions developed here will be useful for their initial synthesis. The performances of components using these are enhanced using open/short circuited resonators, spurlines and stubs. A quasi-static approach has been investigated to obtain simple closed form expressions for a microstrip line with a rectangular aperture in the ground plane. The effect of a rectangular aperture in the ground plane has been incorporated in the commonly used expressions of a regular microstrip line by introducing the concept of an equivalent effective height. The expressions for the effective height microstrip geometries with defected ground are obtained and this has been further extended to various possibilities of two-conductor and three-conductor coupled lines. Analysis of the filters and the couplers are mainly based on the even and odd mode propagation characteristics of coupled lines. This approach is extended in this thesis for three conductor coupled lines. Novel broadband BPFs and couplers and dual band pass filters employing various coupled line configurations and defected ground have been developed in this research work. Most of these components have been implemented on a regular microwave laminate or LTCC medium (planar or multi-layer) and tested for the required RF performances. The experimental results were compared against the analytically computed results based on the circuit models and the full wave simulations using electromagnetic (EM) simulations for the validation. The results are in good agreement. With practical requirements of the organization in mind, additional design elements such as open circuit stubs have been incorporated in some of these designs to achieve the desired performance. It is expected that the wideband filter (3.0GHz to 3.8GHz) and the broadband coupler (4GHz to 6GHz) developed in this thesis work would be deployed in systems developed at the Central Research Laboratory, Bharat Electronics Limited, Bangalore, India. In summary, the present doctoral work strives to (i) establish a simplified analysis method for the microstrip lines and coupled microstrip lines with a rectangular aperture in the ground plane, (ii) extend the even and odd mode analysis of the coupled lines for several new coupled line configurations, (iii) design novel broadband microwave filters, dual band filter and couplers using both these, (iv) fabricate these devices using the planar technologies including LTCC, and (v) validate the analysis and design with important practical applications.