Vibrational predissociation spectroscopy of mass-selected ionic clusters

This thesis presents structural investigations of molecular ions and ionic clusters using vibrational predissociation spectroscopy. Experimentally, a pulsed beam of the mass-selected ion is crossed by a tunable infrared laser beam generated by a Nd:YAG pumped LiNbO_3 optical parametric oscillator. The resulting fragment ion is mass-analyzed and detected, with its intensity as a function of the laser wavelength being the "action" spectrum of the parent ion. In the case of SiH_7^+, we observed a vibrational band centered at 3866 cm^(-1) with clear P, Q, R branches, which is assigned as a perturbed H_2 stretch. The absence of a second H_2 band suggests that the ion forms a symmetric complex with a structure H_2•SiH_3^+•H_2 , in contrast to the species CH_7^+, which has the structure CH_5^+•H_2. The infrared spectra of NO_2^+(H_2O)_n clusters exhibit a marked change with cluster size, indicating that an intracluster reaction occurs with sufficient solvation. Specifically, in NO_2^+(H_2O)_n clusters where n≤3, H_2O binds to a nitronium ion core; but at n=4 the NO_2^+ reacts, transforming the cluster to a new structure of H_3O^+•(H_2O)_(n_2)•HNO_3. For protonated chlorine nitrate, we have observed two distinct isomers previously predicted by ab initio calculations: NO_2^+•(HOC1), the lowest energy isomer, and (ClO)(HO)NO^+, a covalently bonded isomer about 20 kcal/mol higher in energy. Both isomers decompose to NO_2^+ and HOCl upon photo-excitation. These results for HClONO_2^+ lend strong support to the involvement of an ionic mechanism in the reaction of ClONO_2 on polar stratospheric cloud surfaces, a critical step in the dramatic springtime depletion of ozone over Antarctica. Current research activities on halide-solvent clusters and metal-ligand complexes as well as technological improvements of the apparatus are also discussed.

The intergalactic and circumgalactic medium surrounding star-forming galaxies at redshifts 2 < z < 3

We present measurements of the spatial distribution, kinematics, and physical properties of gas in the circumgalactic medium (CGM) of 2.0<z<2.8 UV color-selected galaxies as well as within the 2<z<3 intergalactic medium (IGM). These measurements are derived from Voigt profile decomposition of the full Lyα and Lyβ forest in 15 high-resolution, high signal-to-noise ratio QSO spectra resulting in a catalog of ∼6000 HI absorbers.

Chapter 2 of this thesis focuses on HI surrounding high-z star-forming galaxies drawn from the Keck Baryonic Structure Survey (KBSS). The KBSS is a unique spectroscopic survey of the distant universe designed to explore the details of the connection between galaxies and intergalactic baryons within the same survey volumes. The KBSS combines high-quality background QSO spectroscopy with large densely-sampled galaxy redshift surveys to probe the CGM at scales of ∼50 kpc to a few Mpc. Based on these data, Chapter 2 presents the first quantitative measurements of the distribution, column density, kinematics, and absorber line widths of neutral hydrogen surrounding high-z star-forming galaxies.

Chapter 3 focuses on the thermal properties of the diffuse IGM. This analysis relies on measurements of the ∼6000 absorber line widths to constrain the thermal and turbulent velocities of absorbing "clouds." A positive correlation between the column density of HI and the minimum line width is recovered and implies a temperature-density relation within the low-density IGM for which higher-density regions are hotter, as is predicted by simple theoretical arguments.

Chapter 4 presents new measurements of the opacity of the IGM and CGM to hydrogen-ionizing photons. The chapter begins with a revised measurement of the HI column density distribution based on this new absorption line catalog that, due to the inclusion of high-order Lyman lines, provides the first statistically robust measurement of the frequency of absorbers with HI column densities 14 ≲ log(N_HI/cm^-2) ≲ 17.2. Also presented are the first measurements of the column density distribution of HI within the CGM (50 <d < 300 pkpc) of high-z galaxies. These distributions are used to calculate the total opacity of the IGM and IGM+CGM and to revise previous measurements of the mean free path of hydrogen-ionizing photons within the IGM. This chapter also considers the effect of the surrounding CGM on the transmission of ionizing photons out of the sites of active star-formation and into the IGM.

This thesis concludes with a brief discussion of work in progress focused on understanding the distribution of metals within the CGM of KBSS galaxies. Appendix B discusses my contributions to the MOSFIRE instrumentation project.

Where Tori fear to tread : hypermassive neutron star remnants and absolute event horizons Or topics in computational general relativity

Computational general relativity is a field of study which has reached maturity only within the last decade. This thesis details several studies that elucidate phenomena related to the coalescence of compact object binaries. Chapters 2 and 3 recounts work towards developing new analytical tools for visualizing and reasoning about dynamics in strongly curved spacetimes. In both studies, the results employ analogies with the classical theory of electricity and magnitism, first (Ch. 2) in the post-Newtonian approximation to general relativity and then (Ch. 3) in full general relativity though in the absence of matter sources. In Chapter 4, we examine the topological structure of absolute event horizons during binary black hole merger simulations conducted with the SpEC code. Chapter 6 reports on the progress of the SpEC code in simulating the coalescence of neutron star-neutron star binaries, while Chapter 7 tests the effects of various numerical gauge conditions on the robustness of black hole formation from stellar collapse in SpEC. In Chapter 5, we examine the nature of pseudospectral expansions of non-smooth functions motivated by the need to simulate the stellar surface in Chapters 6 and 7. In Chapter 8, we study how thermal effects in the nuclear equation of state effect the equilibria and stability of hypermassive neutron stars. Chapter 9 presents supplements to the work in Chapter 8, including an examination of the stability question raised in Chapter 8 in greater mathematical detail.

Topics in LIGO-related physics: interferometric speed meters and tidal work

In the quest to develop viable designs for third-generation optical interferometric gravitational-wave detectors, one strategy is to monitor the relative momentum or speed of the test-mass mirrors, rather than monitoring their relative position. The most straightforward design for a speed-meter interferometer that accomplishes this is described and analyzed in Chapter 2. This design (due to Braginsky, Gorodetsky, Khalili, and Thorne) is analogous to a microwave-cavity speed meter conceived by Braginsky and Khalili. A mathematical mapping between the microwave speed meter and the optical interferometric speed meter is developed and used to show (in accord with the speed being a quantum nondemolition observable) that in principle the interferometric speed meter can beat the gravitational-wave standard quantum limit (SQL) by an arbitrarily large amount, over an arbitrarily wide range of frequencies . However, in practice, to reach or beat the SQL, this specific speed meter requires exorbitantly high input light power. The physical reason for this is explored, along with other issues such as constraints on performance due to optical dissipation.

Chapter 3 proposes a more sophisticated version of a speed meter. This new design requires only a modest input power and appears to be a fully practical candidate for third-generation LIGO. It can beat the SQL (the approximate sensitivity of second-generation LIGO interferometers) over a broad range of frequencies (~ 10 to 100 Hz in practice) by a factor h/h_SQL ~ √W^(SQL)_(circ)/W_circ. Here W_circ is the light power circulating in the interferometer arms and W_SQL ≃ 800 kW is the circulating power required to beat the SQL at 100 Hz (the LIGO-II power). If squeezed vacuum (with a power-squeeze factor e^-2R) is injected into the interferometer's output port, the SQL can be beat with a much reduced laser power: h/h_SQL ~ √W^(SQL)_(circ)/W_circe^-2R. For realistic parameters (e^-2R ≃ 10 and W_circ ≃ 800 to 2000 kW), the SQL can be beat by a factor ~ 3 to 4 from 10 to 100 Hz. [However, as the power increases in these expressions, the speed meter becomes more narrow band; additional power and re-optimization of some parameters are required to maintain the wide band.] By performing frequency-dependent homodyne detection on the output (with the aid of two kilometer-scale filter cavities), one can markedly improve the interferometer's sensitivity at frequencies above 100 Hz.

Chapters 2 and 3 are part of an ongoing effort to develop a practical variant of an interferometric speed meter and to combine the speed meter concept with other ideas to yield a promising third- generation interferometric gravitational-wave detector that entails low laser power.

Chapter 4 is a contribution to the foundations for analyzing sources of gravitational waves for LIGO. Specifically, it presents an analysis of the tidal work done on a self-gravitating body (e.g., a neutron star or black hole) in an external tidal field (e.g., that of a binary companion). The change in the mass-energy of the body as a result of the tidal work, or "tidal heating," is analyzed using the Landau-Lifshitz pseudotensor and the local asymptotic rest frame of the body. It is shown that the work done on the body is gauge invariant, while the body-tidal-field interaction energy contained within the body's local asymptotic rest frame is gauge dependent. This is analogous to Newtonian theory, where the interaction energy is shown to depend on how one localizes gravitational energy, but the work done on the body is independent of that localization. These conclusions play a role in analyses, by others, of the dynamics and stability of the inspiraling neutron-star binaries whose gravitational waves are likely to be seen and studied by LIGO.

Magnetic trapping of atomic tritium for neutrino mass measurement

Improved measurement of the neutrino mass via β decay spectroscopy requires the development of new energy measurement techniques and a new β decay source. A promising proposal is to measure the β energy by the frequency of the cyclotron radiation emitted in a magnetic field and to use a high purity atomic tritium source. This thesis examines the feasibility of using a magnetic trap to create and maintain such a source. We demonstrate that the loss rate due to β decay heating is not a limiting factor for the design. We also calculate the loss rate due to evaporative cooling and propose that the tritium can be cooled sufficiently during trap loading as to render this negligible. We further demonstrate a design for the magnetic field which produces a highly uniform field over a large fraction of the trap volume as needed for cyclotron frequency spectroscopy while still providing effective trapping.

The needle in the hundred square degree haystack: The hunt for binary neutron star mergers with LIGO and Palomar Transient Factory

The Advanced LIGO and Virgo experiments are poised to detect gravitational waves (GWs) directly for the first time this decade. The ultimate prize will be joint observation of a compact binary merger in both gravitational and electromagnetic channels. However, GW sky locations that are uncertain by hundreds of square degrees will pose a challenge. I describe a real-time detection pipeline and a rapid Bayesian parameter estimation code that will make it possible to search promptly for optical counterparts in Advanced LIGO. Having analyzed a comprehensive population of simulated GW sources, we describe the sky localization accuracy that the GW detector network will achieve as each detector comes online and progresses toward design sensitivity. Next, in preparation for the optical search with the intermediate Palomar Transient Factory (iPTF), we have developed a unique capability to detect optical afterglows of gamma-ray bursts (GRBs) detected by the Fermi Gamma-ray Burst Monitor (GBM). Its comparable error regions offer a close parallel to the Advanced LIGO problem, but Fermi's unique access to MeV-GeV photons and its near all-sky coverage may allow us to look at optical afterglows in a relatively unexplored part of the GRB parameter space. We present the discovery and broadband follow-up observations (X-ray, UV, optical, millimeter, and radio) of eight GBM-IPTF afterglows. Two of the bursts (GRB 130702A / iPTF13bxl and GRB 140606B / iPTF14bfu) are at low redshift (z=0.145 and z = 0.384, respectively), are sub-luminous with respect to "standard" cosmological bursts, and have spectroscopically confirmed broad-line type Ic supernovae. These two bursts are possibly consistent with mildly relativistic shocks breaking out from the progenitor envelopes rather than the standard mechanism of internal shocks within an ultra-relativistic jet. On a technical level, the GBM--IPTF effort is a prototype for locating and observing optical counterparts of GW events in Advanced LIGO with the Zwicky Transient Facility.

Secondary Organic Aerosol Composition Studies Using Mass Spectrometry

Trace volatile organic compounds emitted by biogenic and anthropogenic sources into the atmosphere can undergo extensive photooxidation to form species with lower volatility. By equilibrium partitioning or reactive uptake, these compounds can nucleate into new aerosol particles or deposit onto already-existing particles to form secondary organic aerosol (SOA). SOA and other atmospheric particulate matter have measurable effects on global climate and public health, making understanding SOA formation a needed field of scientific inquiry. SOA formation can be done in a laboratory setting, using an environmental chamber; under these controlled conditions it is possible to generate SOA from a single parent compound and study the chemical composition of the gas and particle phases. By studying the SOA composition, it is possible to gain understanding of the chemical reactions that occur in the gas phase and particle phase, and identify potential heterogeneous processes that occur at the surface of SOA particles. In this thesis, mass spectrometric methods are used to identify qualitatively and qualitatively the chemical components of SOA derived from the photooxidation of important anthropogenic volatile organic compounds that are associated with gasoline and diesel fuels and industrial activity (C12 alkanes, toluene, and o-, m-, and p-cresols). The conditions under which SOA was generated in each system were varied to explore the effect of NO_x and inorganic seed composition on SOA chemical composition. The structure of the parent alkane was varied to investigate the effect on the functionalization and fragmentation of the resulting oxidation products. Relative humidity was varied in the alkane system as well to measure the effect of increased particle-phase water on condensed-phase reactions. In all systems, oligomeric species, resulting potentially from particle-phase and heterogeneous processes, were identified. Imines produced by reactions between (NH₄)₂SO₄ seed and carbonyl compounds were identified in all systems. Multigenerational photochemistry producing low- and extremely low-volatility organic compounds (LVOC and ELVOC) was reflected strongly in the particle-phase composition as well.

Volatiles in Protoplanetary Disks

Planets are assembled from the gas, dust, and ice in the accretion disks that encircle young stars. Ices of chemical compounds with low condensation temperatures (<200 K), the so-called volatiles, dominate the solid mass reservoir from which planetesimals are formed and are thus available to build the protoplanetary cores of gas/ice giant planets. It has long been thought that the regions near the condensation fronts of volatiles are preferential birth sites of planets. Moreover, the main volatiles in disks are also the main C-and O-containing species in (exo)planetary atmospheres. Understanding the distribution of volatiles in disks and their role in planet-formation processes is therefore of great interest.

This thesis addresses two fundamental questions concerning the nature of volatiles in planet-forming disks: (1) how are volatiles distributed throughout a disk, and (2) how can we use volatiles to probe planet-forming processes in disks? We tackle the first question in two complementary ways. We have developed a novel super-resolution method to constrain the radial distribution of volatiles throughout a disk by combining multi-wavelength spectra. Thanks to the ordered velocity and temperature profiles in disks, we find that detailed constraints can be derived even with spatially and spectrally unresolved data -- provided a wide range of energy levels are sampled. We also employ high-spatial resolution interferometric images at (sub)mm frequencies using the Atacama Large Millimeter Array (ALMA) to directly measure the radial distribution of volatiles.

For the second question, we combine volatile gas emission measurements with those of the dust continuum emission or extinction to understand dust growth mechanisms in disks and disk instabilities at planet-forming distances from the central star. Our observations and models support the idea that the water vapor can be concentrated in regions near its condensation front at certain evolutionary stages in the lifetime of protoplanetary disks, and that fast pebble growth is likely to occur near the condensation fronts of various volatile species.

I. Thermochemistry and reaction kinetics of disolvated protons by ion cyclotron resonance spectroscopy. II. Thermochemical studies of small fluorocarbons by photoionization mass spectrometry

The disolvated proton, H(OH₂)₂⁺ is employed as a chemical reagent in low pressure (˂ 10^-5 torr) investigations by ion cyclotron resonance spectroscopy. Since termolecular reactions are absent at low pressure, disolvated protons are not generally observed. However H(OH₂)₂⁺ is produced in a sequence of bimolecular reactions in mixtures containing H₂O and one of a small number of organohalide precursors. Then a series of hydrated Lewis bases is produced by H₃O⁺ transfer from H(OH₂)₂⁺. In Chapter II, the relative stability of hydrated bases containing heteroatoms of both first and second row elements is determined from the preferred direction of H₃O⁺ transfer between BH(OH₂)⁺ complexes. S and P containing bases are shown to bind H₃O⁺ more weakly than O and N bases with comparable proton affinities. A simple model of hydrogen bonding is proposed to account for these observations.

H⁺ transfer from H(OH₂)₂⁺ to several Lewis bases also occurs at low pressure. In Chapter III the relative importance of H₃O⁺ transfer and H⁺ transfer from H(OH₂)₂⁺ to a series of bases is observed to be a function of base strength. Beginning with CH₃COOH, the weakest base for which H⁺ transfer is observed, the importance of H⁺ transfer increases with increasing proton affinity of the acceptor base. The nature of neutral products formed from H(OH₂)₂⁺ by loss of H⁺ is also considered.

Chapters IV and V deal with thermochemistry of small fluorocarbons determined by photoionization mass spectrometry. The enthalpy of formation of CF₂ is considered in Chapter IV. Photoionization of perfluoropropylene, perfluorocyclopropane, and trifluoromethyl benzene yield onsets for ions formed by loss of a CF₂ neutral fragment. Earlier determinations of ΔH^°_f298 (CF₂) are reinterpreted using updated thermochemical values and compared with results of this study. The heat of formation of neutral perfluorocyclopropane is also derived. Finally, the energetics of interconversion of perfluoropropylene and perfluorocyclopropane are considered for both the neutrals and their molecular ions.

In Chapter V the heats of formation of CF₃⁺ and CF₃I⁺are derived from photoionization of CF₃I. These are considered with respect to ion-molecule reactions observed in CF₃I monitored by the techniques of ion cyclotron resonance spectroscopy. Results obtained in previous experiments are also compared.

I. Current commutators in quantum electrodynamics. II. Electromagnetic mass differences of the pseudoscalar meson and baryon octets

This thesis is in two parts. In the first section, the operator structure of the singular terms in the equal-time commutator of space and time components of the electromagnetic current is investigated in perturbation theory by establishing a connection with Feynman diagrams. It is made very plausible that the singular term is a c number. Some remarks are made about the same problem in the electrodynamics of a spinless particle.

In the second part, an SU(3) symmetric multi-channel calculation of the electromagnetic mass differences in the pseudoscalar meson and baryon octets is carried out with an attempt to include some of the physics of the crossed (pair annihilation) channel along the lines of the recent work by Ball and Zachariasen. The importance of the tensor meson Regge trajectories is emphasized. The agreement with experiment is poor for the isospin one mass differences, but excellent for those with isospin two.

Mechanism of mass transfer in the formation of hydrothermal deposits of sulphides [Translation from: Trudy Inst.Geol.rudn.Mesterozh. 16, 80 [pages 44-46 ”Solubility of sulphides of iron” only], 1958]

This partial translation of the original paper provides the summary of this study of the mechanism of mass transfer in the formation of hydrothermal deposits of sulphides. For determining the solubility of sulphides of iron, the radioactive isotope Fe59 was used. The solubility of two sulphides was determined.

Mass transfer from a cylinder to an air stream in axisymmetrical flow (an experimental study)

Mass transfer from wetted surfaces on one-inch cylinders with unwetted approach sections was studied experimentally by means of the evaporation of n-octane and n-heptane into an air stream in axisymmetrical flow, for Reynolds numbers from 5,000 to 310,000. A transition from the laminar to the turbulent boundary layer was observed to occur at Reynolds numbers from 10,000 to 15,000. The results were expressed in terms of the Sherwood number as a function of the Reynolds number, the Schmidt number, and the ratio of the unwetted approach length to the total length. Empirical formulas were obtained for both laminar and turbulent regimes. The rates of mass transfer obtained were higher than theoretical and experimental results obtained by previous investigators for mass and heat transfer from flat plates.

Part I: Latent heat of vaporization of n-decane. Part II: Heat and mass transfer from a cylinder placed in a turbulent air stream - Sherwood and Frössling numbers as a function of free stream turbulence level and Reynolds number

Part I

The latent heat of vaporization of n-decane is measured calorimetrically at temperatures between 160° and 340°F. The internal energy change upon vaporization, and the specific volume of the vapor at its dew point are calculated from these data and are included in this work. The measurements are in excellent agreement with available data at 77° and also at 345°F, and are presented in graphical and tabular form.

Part II

Simultaneous material and energy transport from a one-inch adiabatic porous cylinder is studied as a function of free stream Reynolds Number and turbulence level. Experimental data is presented for Reynolds Numbers between 1600 and 15,000 based on the cylinder diameter, and for apparent turbulence levels between 1.3 and 25.0 per cent. n-heptane and n-octane are the evaporating fluids used in this investigation.

Gross Sherwood Numbers are calculated from the data and are in substantial agreement with existing correlations of the results of other workers. The Sherwood Numbers, characterizing mass transfer rates, increase approximately as the 0.55 power of the Reynolds Number. At a free stream Reynolds Number of 3700 the Sherwood Number showed a 40% increase as the apparent turbulence level of the free stream was raised from 1.3 to 25 per cent.

Within the uncertainties involved in the diffusion coefficients used for n-heptane and n-octane, the Sherwood Numbers are comparable for both materials. A dimensionless Frössling Number is computed which characterizes either heat or mass transfer rates for cylinders on a comparable basis. The calculated Frössling Numbers based on mass transfer measurements are in substantial agreement with Frössling Numbers calculated from the data of other workers in heat transfer.

On the added mass of sphere in a circular cylinder considering real fluid effects

An experimental method combined with boundary layer theory is given for evaluating the added mass of a sphere moving along the axis of a circular cylinder filled with water or oil. The real fluid effects are separated from ideal fluid effects.

The experimental method consists essentially of a magnetic steel sphere propelled from rest by an electromagnetic coil in which the current is accurately controlled so that it only supplies force for a short time interval which is within the laminar flow regime of the fluid. The motion of the sphere as a function of time is recorded on single frame photographs using a short-arc multiple flash lamp with accurately controlled time intervals between flashes.

A concept of the effect of boundary layer displacement on the fluid flow around a sphere is introduced to evaluate the real fluid effects on the added mass. Surprisingly accurate agreement between experiment and theory is achieved.

Mass measurements of some proton-rich nuclei

The Q values and 0^o cross sections of (He³, n) reactions forming seven proton-rich nuclei have been measured with accuracies varying from 6 to 18 keV. The Q values (in keV) are: Si²⁶ (85), S³⁰ (-573), Ar³⁴ (-759), Ti⁴² (-2865), Cr⁴⁸ (5550), Ni⁵⁶ (4513) and Zn⁶⁰ (818). At least one excited state was found for all but Ti⁴². The first four nuclei complete isotopic spin triplets; the results obtained agree well with charge-symmetry predictions. The last three, all multiples of the α particle, are important in the α and e-process theories of nucleo-synthesis in stars. The energy available for β decay of these three was found by magnetic spectrometer measurements of the (He³, p) Q values of reactions leading to V⁴⁸, Co⁵⁶, and Cu⁶⁰. Many excited states were seen: V⁴⁸ (3), Co⁵⁶ (15), Cu⁶⁰ (23). The first two states of S³⁰ are probably 0⁺ and 2⁺ from (He³, n) angular distribution measurements. Two NaI γ-ray measurements are described: the decay of Ar³⁴ (measured ^Ƭ1/2 = 1.2 ± 0.3s) and the prompt γ-ray spectrum from Fe⁵⁴(He³, nγ)Ni⁵⁶. Possible collective structure in Ni⁵⁶ and Ca⁴⁰, both doubly magic, is discussed.

The (He³, n) neutron energy and yield measurements utilized neutron-induced nuclear reactions in a silicon semiconductor detector. Cross sections for the most important detection processes, Si²⁸ (n, α) Mg²⁵ and Si²⁸ (n, p) Al²⁸, are presented for reactions leading to the first four states of both residual nuclei for neutron energies from 7.3 to 16.4 MeV. Resolution and pulse-height anomalies associated with recoil Mg²⁵ and Al²⁸ ions are discussed. The 0^o cross section for Be⁹ (α, n) C¹², used to provide calibration neutrons, has been measured with a stilbene spectrometer for n_o (5.0 ≤ E_α ≤ 12 MeV), n₁ (4.3 ≤ E_α ≤ 12.0 MeV) and n₂ (6.0 ≤ E_α ≤ 10.1 MeV). Resonances seen in the n_o yield may correspond to nine new levels in C¹³.