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.

Nonlinear optics and wavelength translation via cavity-optomechanics

The field of cavity-optomechanics explores the interaction of light with sound in an ever increasing array of devices. This interaction allows the mechanical system to be both sensed and controlled by the optical system, opening up a wide variety of experiments including the cooling of the mechanical resonator to its quantum mechanical ground state and the squeezing of the optical field upon interaction with the mechanical resonator, to name two.

In this work we explore two very different systems with different types of optomechanical coupling. The first system consists of two microdisk optical resonators stacked on top of each other and separated by a very small slot. The interaction of the disks causes their optical resonance frequencies to be extremely sensitive to the gap between the disks. By careful control of the gap between the disks, the optomechanical coupling can be made to be quadratic to first order which is uncommon in optomechanical systems. With this quadratic coupling the light field is now sensitive to the energy of the mechanical resonator and can directly control the potential energy trapping the mechanical motion. This ability to directly control the spring constant without modifying the energy of the mechanical system, unlike in linear optomechanical coupling, is explored.

Next, the bulk of this thesis deals with a high mechanical frequency optomechanical crystal which is used to coherently convert photons between different frequencies. This is accomplished via the engineered linear optomechanical coupling in these devices. Both classical and quantum systems utilize the interaction of light and matter across a wide range of energies. These systems are often not naturally compatible with one another and require a means of converting photons of dissimilar wavelengths to combine and exploit their different strengths. Here we theoretically propose and experimentally demonstrate coherent wavelength conversion of optical photons using photon-phonon translation in a cavity-optomechanical system. For an engineered silicon optomechanical crystal nanocavity supporting a 4 GHz localized phonon mode, optical signals in a 1.5 MHz bandwidth are coherently converted over a 11.2 THz frequency span between one cavity mode at wavelength 1460 nm and a second cavity mode at 1545 nm with a 93% internal (2% external) peak efficiency. The thermal and quantum limiting noise involved in the conversion process is also analyzed and, in terms of an equivalent photon number signal level, are found to correspond to an internal noise level of only 6 and 4 times 10x^-3 quanta, respectively.

We begin by developing the requisite theoretical background to describe the system. A significant amount of time is then spent describing the fabrication of these silicon nanobeams, with an emphasis on understanding the specifics and motivation. The experimental demonstration of wavelength conversion is then described and analyzed. It is determined that the method of getting photons into the cavity and collected from the cavity is a fundamental limiting factor in the overall efficiency. Finally, a new coupling scheme is designed, fabricated, and tested that provides a means of coupling greater than 90% of photons into and out of the cavity, addressing one of the largest obstacles with the initial wavelength conversion experiment.

Understanding planet formation through high precision photometry and spectroscopy

From studies of protoplanetary disks to extrasolar planets and planetary debris, we aim to understand the full evolution of a planetary system. Observational constraints from ground- and space-based instrumentation allows us to measure the properties of objects near and far and are central to developing this understanding. We present here three observational campaigns that, when combined with theoretical models, reveal characteristics of different stages and remnants of planet formation. The Kuiper Belt provides evidence of chemical and dynamical activity that reveals clues to its primordial environment and subsequent evolution. Large samples of this population can only be assembled at optical wavelengths, with thermal measurements at infrared and sub-mm wavelengths currently available for only the largest and closest bodies. We measure the size and shape of one particular object precisely here, in hopes of better understanding its unique dynamical history and layered composition.

Molecular organic chemistry is one of the most fundamental and widespread facets of the universe, and plays a key role in planet formation. A host of carbon-containing molecules vibrationally emit in the near-infrared when excited by warm gas, T~1000 K. The NIRSPEC instrument at the W.M. Keck Observatory is uniquely configured to study large ranges of this wavelength region at high spectral resolution. Using this facility we present studies of warm CO gas in protoplanetary disks, with a new code for precise excitation modeling. A parameterized suite of models demonstrates the abilities of the code and matches observational constraints such as line strength and shape. We use the models to probe various disk parameters as well, which are easily extensible to others with known disk emission spectra such as water, carbon dioxide, acetylene, and hydrogen cyanide.

Lastly, the existence of molecules in extrasolar planets can also be studied with NIRSPEC and reveals a great deal about the evolution of the protoplanetary gas. The species we observe in protoplanetary disks are also often present in exoplanet atmospheres, and are abundant in Earth's atmosphere as well. Thus, a sophisticated telluric removal code is necessary to analyze these high dynamic range, high-resolution spectra. We present observations of a hot Jupiter, revealing water in its atmosphere and demonstrating a new technique for exoplanet mass determination and atmospheric characterization. We will also be applying this atmospheric removal code to the aforementioned disk observations, to improve our data analysis and probe less abundant species. Guiding models using observations is the only way to develop an accurate understanding of the timescales and processes involved. The futures of the modeling and of the observations are bright, and the end goal of realizing a unified model of planet formation will require both theory and data, from a diverse collection of sources.

Investigation of bulk indium antimonide as heterodyne detector for the submillimeter wavelength region

Bulk n-lnSb is investigated at a heterodyne detector for the submillimeter wavelength region. Two modes or operation are investigated: (1) the Rollin or hot electron bolometer mode (zero magnetic field), and (2) the Putley mode (quantizing magnetic field). The highlight of the thesis work is the pioneering demonstration or the Putley mode mixer at several frequencies. For example, a double-sideband system noise temperature of about 510K was obtained using a 812 GHz methanol laser for the local oscillator. This performance is at least a factor or 10 more sensitive than any other performance reported to date at the same frequency. In addition, the Putley mode mixer achieved system noise temperatures of 250K at 492 GHz and 350K at 625 GHz. The 492 GHz performance is about 50% better and the 625 GHz is about 100% better than previous best performances established by the Rollin-mode mixer. To achieve these results, it was necessary to design a totally new ultra-low noise, room-temperature preamp to handle the higher source impedance imposed by the Putley mode operation. This preamp has considerably less input capacitance than comparably noisy, ambient designs.

In addition to advancing receiver technology, this thesis also presents several novel results regarding the physics of n-lnSb at low temperatures. A Fourier transform spectrometer was constructed and used to measure the submillimeter wave absorption coefficient of relatively pure material at liquid helium temperatures and in zero magnetic field. Below 4.2K, the absorption coefficient was found to decrease with frequency much faster than predicted by Drudian theory. Much better agreement with experiment was obtained using a quantum theory based on inverse-Bremmstrahlung in a solid. Also the noise of the Rollin-mode detector at 4.2K was accurately measured and compared with theory. The power spectrum is found to be well fit by a recent theory of non- equilibrium noise due to Mather. Surprisingly, when biased for optimum detector performance, high purity lnSb cooled to liquid helium temperatures generates less noise than that predicted by simple non-equilibrium Johnson noise theory alone. This explains in part the excellent performance of the Rollin-mode detector in the millimeter wavelength region.

Again using the Fourier transform spectrometer, spectra are obtained of the responsivity and direct detection NEP as a function of magnetic field in the range 20-110 cm^-1. The results show a discernable peak in the detector response at the conduction electron cyclotron resonance frequency tor magnetic fields as low as 3 KG at bath temperatures of 2.0K. The spectra also display the well-known peak due to the cyclotron resonance of electrons bound to impurity states. The magnitude of responsivity at both peaks is roughly constant with magnet1c field and is comparable to the low frequency Rollin-mode response. The NEP at the peaks is found to be much better than previous values at the same frequency and comparable to the best long wavelength results previously reported. For example, a value NEP=4.5x10^-13/Hz^1/2 is measured at 4.2K, 6 KG and 40 cm^-1. Study of the responsivity under conditions of impact ionization showed a dramatic disappearance of the impurity electron resonance while the conduction electron resonance remained constant. This observation offers the first concrete evidence that the mobility of an electron in the N=0 and N=1 Landau levels is different. Finally, these direct detection experiments indicate that the excellent heterodyne performance achieved at 812 GHz should be attainable up to frequencies of at least 1200 GHz.

Nonclassical excitation and quantum interference in a three level atom

Non-classical properties and quantum interference (QI) in two-photon excitation of a three level atom (|1〉), |2〉, |3〉) in a ladder configuration, illuminated by multiple fields in non-classical (squeezed) and/or classical (coherent) states, is studied. Fundamentally new effects associated with quantum correlations in the squeezed fields and QI due to multiple excitation pathways have been observed. Theoretical studies and extrapolations of these findings have revealed possible applications which are far beyond any current capabilities, including ultrafast nonlinear mixing, ultrafast homodyne detection and frequency metrology. The atom used throughout the experiments was Cesium, which was magneto-optically trapped in a vapor cell to produce a Doppler-free sample. For the first part of the work the |1〉 → |2〉 → |3〉 transition (corresponding to the 6S_1/2F = 4 → 6P_3/2F' = 5 → 6D_5/2F" = 6 transition) was excited by using the quantum-correlated signal (Ɛ_s) and idler (Ɛ_i) output fields of a subthreshold non-degenerate optical parametric oscillator, which was tuned so that the signal and idler fields were resonant with the |1〉 → |2〉 and |2〉 → |3〉 transitions, respectively. In contrast to excitation with classical fields for which the excitation rate as a function of intensity has always an exponent greater than or equal to two, excitation with squeezed-fields has been theoretically predicted to have an exponent that approaches unity for small enough intensities. This was verified experimentally by probing the exponent down to a slope of 1.3, demonstrating for the first time a purely non-classical effect associated with the interaction of squeezed fields and atoms. In the second part excitation of the two-photon transition by three phase coherent fields Ɛ₁ , Ɛ₂ and Ɛ₀, resonant with the dipole |1〉 → |2〉 and |2〉 → |3〉 and quadrupole |1〉 → |3〉 transitions, respectively, is studied. QI in the excited state population is observed due to two alternative excitation pathways. This is equivalent to nonlinear mixing of the three excitation fields by the atom. Realizing that in the experiment the three fields are spaced in frequency over a range of 25 THz, and extending this scheme to other energy triplets and atoms, leads to the discovery that ranges up to 100's of THz can be bridged in a single mixing step. Motivated by these results, a master equation model has been developed for the system and its properties have been extensively studied.

Design of antenna-coupled lumped-element titanium nitride KIDs for long-wavelength multi-band continuum imaging

Many applications in cosmology and astrophysics at millimeter wavelengths including CMB polarization, studies of galaxy clusters using the Sunyaev-Zeldovich effect (SZE), and studies of star formation at high redshift and in our local universe and our galaxy, require large-format arrays of millimeter-wave detectors. Feedhorn and phased-array antenna architectures for receiving mm-wave light present numerous advantages for control of systematics, for simultaneous coverage of both polarizations and/or multiple spectral bands, and for preserving the coherent nature of the incoming light. This enables the application of many traditional "RF" structures such as hybrids, switches, and lumped-element or microstrip band-defining filters.

Simultaneously, kinetic inductance detectors (KIDs) using high-resistivity materials like titanium nitride are an attractive sensor option for large-format arrays because they are highly multiplexable and because they can have sensitivities reaching the condition of background-limited detection. A KID is a LC resonator. Its inductance includes the geometric inductance and kinetic inductance of the inductor in the superconducting phase. A photon absorbed by the superconductor breaks a Cooper pair into normal-state electrons and perturbs its kinetic inductance, rendering it a detector of light. The responsivity of KID is given by the fractional frequency shift of the LC resonator per unit optical power.

However, coupling these types of optical reception elements to KIDs is a challenge because of the impedance mismatch between the microstrip transmission line exiting these architectures and the high resistivity of titanium nitride. Mitigating direct absorption of light through free space coupling to the inductor of KID is another challenge. We present a detailed titanium nitride KID design that addresses these challenges. The KID inductor is capacitively coupled to the microstrip in such a way as to form a lossy termination without creating an impedance mismatch. A parallel plate capacitor design mitigates direct absorption, uses hydrogenated amorphous silicon, and yields acceptable noise. We show that the optimized design can yield expected sensitivities very close to the fundamental limit for a long wavelength imager (LWCam) that covers six spectral bands from 90 to 400 GHz for SZE studies.

Excess phase (frequency) noise has been observed in KID and is very likely caused by two-level systems (TLS) in dielectric materials. The TLS hypothesis is supported by the measured dependence of the noise on resonator internal power and temperature. However, there is still a lack of a unified microscopic theory which can quantitatively model the properties of the TLS noise. In this thesis we derive the noise power spectral density due to the coupling of TLS with phonon bath based on an existing model and compare the theoretical predictions about power and temperature dependences with experimental data. We discuss the limitation of such a model and propose the direction for future study.

Excitation energies and decay properties of T = 3/2 states in ^(17)O, ^(17)F and ^(21)Na

The two lowest T = 3/2 levels in ²¹Na have been studied in the ¹⁹F(³He, n), ²⁰Ne (p,p) and ²⁰Ne (p,p’) reactions, and their excitation energies, spins, parities and widths have been determined. In a separate investigation, branching ratios were measured for the isospin-nonconserving particle decays of the lowest T = 3/2 levels in ¹⁷O and ¹⁷F to the ground state and first two excited states of ¹⁶O, by studying the ¹⁵N(³He,n) ¹⁷F*(p) ¹⁶O and ¹⁸O(³He, α)¹⁷O*(n) ¹⁶O reactions.

The ¹⁹F(³He,n) ²¹Na reaction was studied at incident energies between 4.2 and 5.9 MeV using a pulsed-beam neutron-time-of-flight spectrometer. Two T = 3/2 levels were identified at excitation energies of 8.99 ± 0.05 MeV (J > ½) and 9.22 ± 0.015 MeV (J ^π = ½⁺, Γ ˂ 40 keV). The spins and parities were determined by a comparison of the measured angular distributions with the results of DWBA calculations.

These two levels were also obsesrved as isospin-forbidden resonances in the ²⁰Ne(p,p) and ²⁰Ne(p,p’) reactions. Excitation energies were measured and spins, parities, and widths were determined from a single level dispersion theory analysis. The following results were obtained:

E_x = 8.973 ± 0.007 MeV, J ^π = 5/2 ⁺ or 3/2⁺, Γ ≤ 1.2 keV,

^Γp_o = 0.1 ± 0.05 keV; E_x = 9.217 ± 0.007 MeV, J^π = ½ ⁺,

Γ = 2.3 ± 0.5 keV, ^Γp_o = 1.1 ± 0.3 keV.

Isospin assignments were made on the basis of excitation energies, spins, parities, and widths.

Branching ratios for the isospin-nonconserving proton decays of the 11.20 MeV, T = 3/2 level in ¹⁷F were measured by the ¹⁵N(³He,n) ¹⁷ F*(p) ¹⁶O reaction to be 0.088 ± 0.016 to the ground state of ¹⁶O and 0.22 ± 0.04 to the unresolved 6.05 and 6.13 MeV levels of ¹⁶O. Branching ratios for the neutron decays of the analogous T = 3/2 level, at 11.08 MeV in ¹⁷O, were measured by the ¹⁶O(³He, α)¹⁷O*(n)¹⁶O reaction to be 0.91 ± 0.15 to the ground state of ¹⁶O and 0.05 ± 0.02 to the unresolved 6.05 and 6.13 MeV states. By comparing the ratios of reduced widths for the mirror decays, the form of the isospin impurity in the T = 3/2 levels is shown to depend on T_z.