Terahertz time domain spectroscopy of amino acids and sugars

A time-domain spectrometer for use in the terahertz (THz) spectral range was designed and constructed. Due to there being few existing methods of generating and detecting THz radiation, the spectrometer is expected to have vast applications to solid, liquid, and gas phase samples. In particular, knowledge of complex organic chemistry and chemical abundances in the interstellar medium (ISM) can be obtained when compared to astronomical data. The THz spectral region is of particular interest due to reduced line density when compared to the millimeter wave spectrum, the existence of high resolution observatories, and potentially strong transitions resulting from the lowest-lying vibrational modes of large molecules.

The heart of the THz time-domain spectrometer (THz-TDS) is the ultrafast laser. Due to the femtosecond duration of ultrafast laser pulses and an energy-time uncertainty relationship, the pulses typically have a several-THz bandwidth. By various means of optical rectification, the optical pulse carrier envelope shape, i.e. intensity-time profile, can be transferred to the phase of the resulting THz pulse. As a consequence, optical pump-THz probe spectroscopy is readily achieved, as was demonstrated in studies of dye-sensitized TiO₂, as discussed in chapter 4. Detection of the terahertz radiation is commonly based on electro-optic sampling and provides full phase information. This allows for accurate determination of both the real and imaginary index of refraction, the so-called optical constants, without additional analysis. A suite of amino acids and sugars, all of which have been found in meteorites, were studied in crystalline form embedded in a polyethylene matrix. As the temperature was varied between 10 and 310 K, various strong vibrational modes were found to shift in spectral intensity and frequency. Such modes can be attributed to intramolecular, intermolecular, or phonon modes, or to some combination of the three.

Optimal uncertainty quantification via convex optimization and relaxation

Many engineering applications face the problem of bounding the expected value of a quantity of interest (performance, risk, cost, etc.) that depends on stochastic uncertainties whose probability distribution is not known exactly. Optimal uncertainty quantification (OUQ) is a framework that aims at obtaining the best bound in these situations by explicitly incorporating available information about the distribution. Unfortunately, this often leads to non-convex optimization problems that are numerically expensive to solve.

This thesis emphasizes on efficient numerical algorithms for OUQ problems. It begins by investigating several classes of OUQ problems that can be reformulated as convex optimization problems. Conditions on the objective function and information constraints under which a convex formulation exists are presented. Since the size of the optimization problem can become quite large, solutions for scaling up are also discussed. Finally, the capability of analyzing a practical system through such convex formulations is demonstrated by a numerical example of energy storage placement in power grids.

When an equivalent convex formulation is unavailable, it is possible to find a convex problem that provides a meaningful bound for the original problem, also known as a convex relaxation. As an example, the thesis investigates the setting used in Hoeffding's inequality. The naive formulation requires solving a collection of non-convex polynomial optimization problems whose number grows doubly exponentially. After structures such as symmetry are exploited, it is shown that both the number and the size of the polynomial optimization problems can be reduced significantly. Each polynomial optimization problem is then bounded by its convex relaxation using sums-of-squares. These bounds are found to be tight in all the numerical examples tested in the thesis and are significantly better than Hoeffding's bounds.

Part I. A study of the velocity structure of the earth by the use of core phases. Part II. The 1971 San Fernando earthquake series focal mechanisms and tectonics

The initial objective of Part I was to determine the nature of upper mantle discontinuities, the average velocities through the mantle, and differences between mantle structure under continents and oceans by the use of P'dP', the seismic core phase P'P' (PKPPKP) that reflects at depth d in the mantle. In order to accomplish this, it was found necessary to also investigate core phases themselves and their inferences on core structure. P'dP' at both single stations and at the LASA array in Montana indicates that the following zones are candidates for discontinuities with varying degrees of confidence: 800-950 km, weak; 630-670 km, strongest; 500-600 km, strong but interpretation in doubt; 350-415 km, fair; 280-300 km, strong, varying in depth; 100-200 km, strong, varying in depth, may be the bottom of the low-velocity zone. It is estimated that a single station cannot easily discriminate between asymmetric P'P' and P'dP' for lead times of about 30 sec from the main P'P' phase, but the LASA array reduces this uncertainty range to less than 10 sec. The problems of scatter of P'P' main-phase times, mainly due to asymmetric P'P', incorrect identification of the branch, and lack of the proper velocity structure at the velocity point, are avoided and the analysis shows that one-way travel of P waves through oceanic mantle is delayed by 0.65 to 0.95 sec relative to United States mid-continental mantle.

A new P-wave velocity core model is constructed from observed times, dt/dΔ's, and relative amplitudes of P'; the observed times of SKS, SKKS, and PKiKP; and a new mantle-velocity determination by Jordan and Anderson. The new core model is smooth except for a discontinuity at the inner-core boundary determined to be at a radius of 1215 km. Short-period amplitude data do not require the inner core Q to be significantly lower than that of the outer core. Several lines of evidence show that most, if not all, of the arrivals preceding the DF branch of P' at distances shorter than 143° are due to scattering as proposed by Haddon and not due to spherically symmetric discontinuities just above the inner core as previously believed. Calculation of the travel-time distribution of scattered phases and comparison with published data show that the strongest scattering takes place at or near the core-mantle boundary close to the seismic station.

In Part II, the largest events in the San Fernando earthquake series, initiated by the main shock at 14 00 41.8 GMT on February 9, 1971, were chosen for analysis from the first three months of activity, 87 events in all. The initial rupture location coincides with the lower, northernmost edge of the main north-dipping thrust fault and the aftershock distribution. The best focal mechanism fit to the main shock P-wave first motions constrains the fault plane parameters to: strike, N 67° (± 6°) W; dip, 52° (± 3°) NE; rake, 72° (67°-95°) left lateral. Focal mechanisms of the aftershocks clearly outline a downstep of the western edge of the main thrust fault surface along a northeast-trending flexure. Faulting on this downstep is left-lateral strike-slip and dominates the strain release of the aftershock series, which indicates that the downstep limited the main event rupture on the west. The main thrust fault surface dips at about 35° to the northeast at shallow depths and probably steepens to 50° below a depth of 8 km. This steep dip at depth is a characteristic of other thrust faults in the Transverse Ranges and indicates the presence at depth of laterally-varying vertical forces that are probably due to buckling or overriding that causes some upward redirection of a dominant north-south horizontal compression. Two sets of events exhibit normal dip-slip motion with shallow hypocenters and correlate with areas of ground subsidence deduced from gravity data. Several lines of evidence indicate that a horizontal compressional stress in a north or north-northwest direction was added to the stresses in the aftershock area 12 days after the main shock. After this change, events were contained in bursts along the downstep and sequencing within the bursts provides evidence for an earthquake-triggering phenomenon that propagates with speeds of 5 to 15 km/day. Seismicity before the San Fernando series and the mapped structure of the area suggest that the downstep of the main fault surface is not a localized discontinuity but is part of a zone of weakness extending from Point Dume, near Malibu, to Palmdale on the San Andreas fault. This zone is interpreted as a decoupling boundary between crustal blocks that permits them to deform separately in the prevalent crustal-shortening mode of the Transverse Ranges region.

A probabilistic treatment of uncertainty in nonlinear dynamical systems

In this work, computationally efficient approximate methods are developed for analyzing uncertain dynamical systems. Uncertainties in both the excitation and the modeling are considered and examples are presented illustrating the accuracy of the proposed approximations.

For nonlinear systems under uncertain excitation, methods are developed to approximate the stationary probability density function and statistical quantities of interest. The methods are based on approximating solutions to the Fokker-Planck equation for the system and differ from traditional methods in which approximate solutions to stochastic differential equations are found. The new methods require little computational effort and examples are presented for which the accuracy of the proposed approximations compare favorably to results obtained by existing methods. The most significant improvements are made in approximating quantities related to the extreme values of the response, such as expected outcrossing rates, which are crucial for evaluating the reliability of the system.

Laplace's method of asymptotic approximation is applied to approximate the probability integrals which arise when analyzing systems with modeling uncertainty. The asymptotic approximation reduces the problem of evaluating a multidimensional integral to solving a minimization problem and the results become asymptotically exact as the uncertainty in the modeling goes to zero. The method is found to provide good approximations for the moments and outcrossing rates for systems with uncertain parameters under stochastic excitation, even when there is a large amount of uncertainty in the parameters. The method is also applied to classical reliability integrals, providing approximations in both the transformed (independently, normally distributed) variables and the original variables. In the transformed variables, the asymptotic approximation yields a very simple formula for approximating the value of SORM integrals. In many cases, it may be computationally expensive to transform the variables, and an approximation is also developed in the original variables. Examples are presented illustrating the accuracy of the approximations and results are compared with existing approximations.

Accelerogram processing using reliability bounds and optimal correction methods

This study addresses the problem of obtaining reliable velocities and displacements from accelerograms, a concern which often arises in earthquake engineering. A closed-form acceleration expression with random parameters is developed to test any strong-motion accelerogram processing method. Integration of this analytical time history yields the exact velocities, displacements and Fourier spectra. Noise and truncation can also be added. A two-step testing procedure is proposed and the original Volume II routine is used as an illustration. The main sources of error are identified and discussed. Although these errors may be reduced, it is impossible to extract the true time histories from an analog or digital accelerogram because of the uncertain noise level and missing data. Based on these uncertainties, a probabilistic approach is proposed as a new accelerogram processing method. A most probable record is presented as well as a reliability interval which reflects the level of error-uncertainty introduced by the recording and digitization process. The data is processed in the frequency domain, under assumptions governing either the initial value or the temporal mean of the time histories. This new processing approach is tested on synthetic records. It induces little error and the digitization noise is adequately bounded. Filtering is intended to be kept to a minimum and two optimal error-reduction methods are proposed. The "noise filters" reduce the noise level at each harmonic of the spectrum as a function of the signal-to-noise ratio. However, the correction at low frequencies is not sufficient to significantly reduce the drifts in the integrated time histories. The "spectral substitution method" uses optimization techniques to fit spectral models of near-field, far-field or structural motions to the amplitude spectrum of the measured data. The extremes of the spectrum of the recorded data where noise and error prevail are then partly altered, but not removed, and statistical criteria provide the choice of the appropriate cutoff frequencies. This correction method has been applied to existing strong-motion far-field, near-field and structural data with promising results. Since this correction method maintains the whole frequency range of the record, it should prove to be very useful in studying the long-period dynamics of local geology and structures.

Crystal Coulomb energies: I. Organic donor-acceptor complexes--a review. II. Classical Ewald calculations of the Coulomb binding energy of four donor-acceptor crystals and Wurster's blue perchlorate. III. A rapid-convergence quantum-mechanical formalism for crystal electronic energies

Chapter I

Theories for organic donor-acceptor (DA) complexes in solution and in the solid state are reviewed, and compared with the available experimental data. As shown by McConnell et al. (Proc. Natl. Acad. Sci. U.S., 53, 46-50 (1965)), the DA crystals fall into two classes, the holoionic class with a fully or almost fully ionic ground state, and the nonionic class with little or no ionic character. If the total lattice binding energy 2ε₁ (per DA pair) gained in ionizing a DA lattice exceeds the cost 2ε_o of ionizing each DA pair, ε₁ + ε_o less than 0, then the lattice is holoionic. The charge-transfer (CT) band in crystals and in solution can be explained, following Mulliken, by a second-order mixing of states, or by any theory that makes the CT transition strongly allowed, and yet due to a small change in the ground state of the non-interacting components D and A (or D⁺ and A^-). The magnetic properties of the DA crystals are discussed.

Chapter II

A computer program, EWALD, was written to calculate by the Ewald fast-convergence method the crystal Coulomb binding energy E_C due to classical monopole-monopole interactions for crystals of any symmetry. The precision of E_C values obtained is high: the uncertainties, estimated by the effect on E_C of changing the Ewald convergence parameter η, ranged from ± 0.00002 eV to ± 0.01 eV in the worst case. The charge distribution for organic ions was idealized as fractional point charges localized at the crystallographic atomic positions: these charges were chosen from available theoretical and experimental estimates. The uncertainty in E_C due to different charge distribution models is typically ± 0.1 eV (± 3%): thus, even the simple Hückel model can give decent results.

E_C for Wurster's Blue Perchl orate is -4.1 eV/molecule: the crystal is stable under the binding provided by direct Coulomb interactions. E_C for N-Methylphenazinium Tetracyanoquino- dimethanide is 0.1 eV: exchange Coulomb interactions, which cannot be estimated classically, must provide the necessary binding.

EWALD was also used to test the McConnell classification of DA crystals. For the holoionic (1:1)-(N,N,N',N'-Tetramethyl-para- phenylenediamine: 7,7,8,8-Tetracyanoquinodimethan) E_C = -4.0 eV while 2ε_o = 4.6₅ eV: clearly, exchange forces must provide the balance. For the holoionic (1:1)-(N,N,N',N'-Tetramethyl-para- phenylenediamine:para-Chloranil) E_C = -4.4 eV, while 2ε_o = 5.0 eV: again EC falls short of 2ε₁. As a Gedankenexperiment, two nonionic crystals were assumed to be ionized: for (1:1)-(Hexamethyl- benzene:para-Chloranil) E_C = -4.5 eV, 2ε_o = 6.6 eV; for (1:1)- (Napthalene:Tetracyanoethylene) E_C = -4.3 eV, 2ε_o = 6.5 eV. Thus, exchange energies in these nonionic crystals must not exceed 1 eV.

Chapter III

A rapid-convergence quantum-mechanical formalism is derived to calculate the electronic energy of an arbitrary molecular (or molecular-ion) crystal: this provides estimates of crystal binding energies which include the exchange Coulomb inter- actions. Previously obtained LCAO-MO wavefunctions for the isolated molecule(s) ("unit cell spin-orbitals") provide the starting-point. Bloch's theorem is used to construct "crystal spin-orbitals". Overlap between the unit cell orbitals localized in different unit cells is neglected, or is eliminated by Löwdin orthogonalization. Then simple formulas for the total kinetic energy Q^(XT)_λ, nuclear attraction [λ/λ]^XT, direct Coulomb [λλ/λ'λ']^XT and exchange Coulomb [λλ'/λ'λ]^XT integrals are obtained, and direct-space brute-force expansions in atomic wavefunctions are given. Fourier series are obtained for [λ/λ]^XT, [λλ/λ'λ']^XT, and [λλ/λ'λ]^XT with the help of the convolution theorem; the Fourier coefficients require the evaluation of Silverstone's two-center Fourier transform integrals. If the short-range interactions are calculated by brute-force integrations in direct space, and the long-range effects are summed in Fourier space, then rapid convergence is possible for [λ/λ]^XT, [λλ/λ'λ']^XT and [λλ'/λ'λ]^XT. This is achieved, as in the Ewald method, by modifying each atomic wavefunction by a "Gaussian convergence acceleration factor", and evaluating separately in direct and in Fourier space appropriate portions of [λ/λ]^XT, etc., where some of the portions contain the Gaussian factor.

Future of earthquake early warning : quantifying uncertainty and making fast automated decisions for applications

Earthquake early warning (EEW) systems have been rapidly developing over the past decade. Japan Meteorological Agency (JMA) has an EEW system that was operating during the 2011 M9 Tohoku earthquake in Japan, and this increased the awareness of EEW systems around the world. While longer-time earthquake prediction still faces many challenges to be practical, the availability of shorter-time EEW opens up a new door for earthquake loss mitigation. After an earthquake fault begins rupturing, an EEW system utilizes the first few seconds of recorded seismic waveform data to quickly predict the hypocenter location, magnitude, origin time and the expected shaking intensity level around the region. This early warning information is broadcast to different sites before the strong shaking arrives. The warning lead time of such a system is short, typically a few seconds to a minute or so, and the information is uncertain. These factors limit human intervention to activate mitigation actions and this must be addressed for engineering applications of EEW. This study applies a Bayesian probabilistic approach along with machine learning techniques and decision theories from economics to improve different aspects of EEW operation, including extending it to engineering applications.

Existing EEW systems are often based on a deterministic approach. Often, they assume that only a single event occurs within a short period of time, which led to many false alarms after the Tohoku earthquake in Japan. This study develops a probability-based EEW algorithm based on an existing deterministic model to extend the EEW system to the case of concurrent events, which are often observed during the aftershock sequence after a large earthquake.

To overcome the challenge of uncertain information and short lead time of EEW, this study also develops an earthquake probability-based automated decision-making (ePAD) framework to make robust decision for EEW mitigation applications. A cost-benefit model that can capture the uncertainties in EEW information and the decision process is used. This approach is called the Performance-Based Earthquake Early Warning, which is based on the PEER Performance-Based Earthquake Engineering method. Use of surrogate models is suggested to improve computational efficiency. Also, new models are proposed to add the influence of lead time into the cost-benefit analysis. For example, a value of information model is used to quantify the potential value of delaying the activation of a mitigation action for a possible reduction of the uncertainty of EEW information in the next update. Two practical examples, evacuation alert and elevator control, are studied to illustrate the ePAD framework. Potential advanced EEW applications, such as the case of multiple-action decisions and the synergy of EEW and structural health monitoring systems, are also discussed.

Essays in optimal resource allocation under uncertainty with capacity constraints

This thesis brings together four papers on optimal resource allocation under uncertainty with capacity constraints. The first is an extension of the Arrow-Debreu contingent claim model to a good subject to supply uncertainty for which delivery capacity has to be chosen before the uncertainty is resolved. The second compares an ex-ante contingent claims market to a dynamic market in which capacity is chosen ex-ante and output and consumption decisions are made ex-post. The third extends the analysis to a storable good subject to random supply. Finally, the fourth examines optimal allocation of water under an appropriative rights system.

An investigation of techniques for the measurement and interpretation of cosmic ray isotopic abundances

An instrument, the Caltech High Energy Isotope Spectrometer Telescope (HEIST), has been developed to measure isotopic abundances of cosmic ray nuclei in the charge range 3 ≤ Z ≤ 28 and the energy range between 30 and 800 MeV/nuc by employing an energy loss -- residual energy technique. Measurements of particle trajectories and energy losses are made using a multiwire proportional counter hodoscope and a stack of CsI(TI) crystal scintillators, respectively. A detailed analysis has been made of the mass resolution capabilities of this instrument.

Landau fluctuations set a fundamental limit on the attainable mass resolution, which for this instrument ranges between ~.07 AMU for z~3 and ~.2 AMU for z~2b. Contributions to the mass resolution due to uncertainties in measuring the path-length and energy losses of the detected particles are shown to degrade the overall mass resolution to between ~.1 AMU (z~3) and ~.3 AMU (z~2b).

A formalism, based on the leaky box model of cosmic ray propagation, is developed for obtaining isotopic abundance ratios at the cosmic ray sources from abundances measured in local interstellar space for elements having three or more stable isotopes, one of which is believed to be absent at the cosmic ray sources. This purely secondary isotope is used as a tracer of secondary production during propagation. This technique is illustrated for the isotopes of the elements O, Ne, S, Ar and Ca.

The uncertainties in the derived source ratios due to errors in fragmentation and total inelastic cross sections, in observed spectral shapes, and in measured abundances are evaluated. It is shown that the dominant sources of uncertainty are uncorrelated errors in the fragmentation cross sections and statistical uncertainties in measuring local interstellar abundances.

These results are applied to estimate the extent to which uncertainties must be reduced in order to distinguish between cosmic ray production in a solar-like environment and in various environments with greater neutron enrichments.

Range of validity of the method of averaging

Sufficient conditions are derived for the validity of approximate periodic solutions of a class of second order ordinary nonlinear differential equations. An approximate solution is defined to be valid if an exact solution exists in a neighborhood of the approximation.

Two classes of validity criteria are developed. Existence is obtained using the contraction mapping principle in one case, and the Schauder-Leray fixed point theorem in the other. Both classes of validity criteria make use of symmetry properties of periodic functions, and both classes yield an upper bound on a norm of the difference between the approximate and exact solution. This bound is used in a procedure which establishes sufficient stability conditions for the approximated solution.

Application to a system with piecewise linear restoring force (bilinear system) reveals that the approximate solution obtained by the method of averaging is valid away from regions where the response exhibits vertical tangents. A narrow instability region is obtained near one-half the natural frequency of the equivalent linear system. Sufficient conditions for the validity of resonant solutions are also derived, and two term harmonic balance approximate solutions which exhibit ultraharmonic and subharmonic resonances are studied.

Experimental study study of antiproton-proton annihilation into a pair of charged Pi-Mesons or K-Mesons for incident antiproton mementa in the range from 0.72 GeV/c to 2.62 GeV/c

The cross sections for the two antiproton-proton annihilation-in-flight modes,

ˉp + p → π⁺ + π^-

ˉp + p → k⁺ + k^-

were measured for fifteen laboratory antiproton beam momenta ranging from 0.72 to 2.62 GeV/c. No magnets were used to determine the charges in the final state. As a result, the angular distributions were obtained in the form [dσ/dΩ (Θ_C.M.) + dσ/dΩ (π – Θ_C.M.)] for 45 ≲ Θ_C.M. ≲ 135°.

A hodoscope-counter system was used to discriminate against events with final states having more than two particles and antiproton-proton elastic scattering events. One spark chamber was used to record the track of each of the two charged final particles. A total of about 40,000 pictures were taken. The events were analyzed by measuring the laboratory angle of the track in each chamber. The value of the square of the mass of the final particles was calculated for each event assuming the reaction

ˉp + p → a pair of particles with equal masses.

About 20,000 events were found to be either annihilation into π ^±-pair or k ^±-pair events. The two different charged meson pair modes were also distinctly separated.

The average differential cross section of ˉp + p → π⁺ + π^- varied from ~ 25 µb/sr at antiproton beam momentum 0.72 GeV/c (total energy in center-of-mass system, √s = 2.0 GeV) to ~ 2 µb/sr at beam momentum 2.62 GeV/c (√s = 2.64 GeV). The most striking feature in the angular distribution was a peak at Θ_C.M. = 90° (cos Θ_C.M. = 0) which increased with √s and reached a maximum at √s ~ 2.1 GeV (beam momentum ~ 1.1 GeV/c). Then it diminished and seemed to disappear completely at √s ~ 2.5 GeV (beam momentum ~ 2.13 GeV/c). A valley in the angular distribution occurred at cos Θ_C.M. ≈ 0.4. The differential cross section then increased as cos Θ_C.M. approached 1.

The average differential cross section for ˉp + p → k⁺ + k^- was about one third of that of the π^±-pair mode throughout the energy range of this experiment. At the lower energies, the angular distribution, unlike that of the π^±-pair mode, was quite isotropic. However, a peak at Θ_C.M. = 90° seemed to develop at √s ~ 2.37 GeV (antiproton beam momentum ~ 1.82 GeV/c). No observable change was seen at that energy in the π^±-pair cross section.

The possible connection of these features with the observed meson resonances at 2.2 GeV and 2.38 GeV, and its implications, were discussed.

Measurements of mantle velocities of P waves with a large array

A large array has been used to investigate the P-wave velocity structure of the lower mantle. Linear array processing methods are reviewed and a method of nonlinear processing is presented. Phase velocities, travel times, and relative amplitudes of P waves have been measured with the large array at the Tonto Forest Seismological Observatory in Arizona for 125 earthquakes in the distance range of 30 to 100 degrees. Various models are assumed for the upper 771 km of the mantle and the Wiechert-Herglotz method applied to the phase velocity data to obtain a velocity depth structure for the lower mantle. The phase velocity data indicates the presence of a second-order discontinuity at a depth of 840 km, another at 1150 km, and less pronounced discontinuities at 1320, 1700 and 1950 km. Phase velocities beyond 85 degrees are interpreted in terms of a triplication of the phase velocity curve, and this results in a zone of almost constant velocity between depths of 2670 and 2800 km. Because of the uncertainty in the upper mantle assumptions, a final model cannot be proposed, but it appears that the lower mantle is more complicated than the standard models and there is good evidence for second-order discontinuities below a depth of 1000 km. A tentative lower bound of 2881 km can be placed on the depth to the core. The importance of checking the calculated velocity structure against independently measured travel times is pointed out. Comparisons are also made with observed PcP times and the agreement is good. The method of using measured values of the rate of change of amplitude with distances shows promising results.