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Time-Domain TeraHertz Spectroscopy and Observational Probes of Prebiotic Interstellar Gas and Ice Chemistry


McGuire, Brett Andrew (2015) Time-Domain TeraHertz Spectroscopy and Observational Probes of Prebiotic Interstellar Gas and Ice Chemistry. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/Z9B27S79.


Understanding the origin of life on Earth has long fascinated the minds of the global community, and has been a driving factor in interdisciplinary research for centuries. Beyond the pioneering work of Darwin, perhaps the most widely known study in the last century is that of Miller and Urey, who examined the possibility of the formation of prebiotic chemical precursors on the primordial Earth [1]. More recent studies have shown that amino acids, the chemical building blocks of the biopolymers that comprise life as we know it on Earth, are present in meteoritic samples, and that the molecules extracted from the meteorites display isotopic signatures indicative of an extraterrestrial origin [2]. The most recent major discovery in this area has been the detection of glycine (NH2CH2COOH), the simplest amino acid, in pristine cometary samples returned by the NASA STARDUST mission [3]. Indeed, the open questions left by these discoveries, both in the public and scientific communities, hold such fascination that NASA has designated the understanding of our "Cosmic Origins" as a key mission priority.

Despite these exciting discoveries, our understanding of the chemical and physical pathways to the formation of prebiotic molecules is woefully incomplete. This is largely because we do not yet fully understand how the interplay between grain-surface and sub-surface ice reactions and the gas-phase affects astrophysical chemical evolution, and our knowledge of chemical inventories in these regions is incomplete. The research presented here aims to directly address both these issues, so that future work to understand the formation of prebiotic molecules has a solid foundation from which to work.

From an observational standpoint, a dedicated campaign to identify hydroxylamine (NH2OH), potentially a direct precursor to glycine, in the gas-phase was undertaken. No trace of NH2OH was found. These observations motivated a refinement of the chemical models of glycine formation, and have largely ruled out a gas-phase route to the synthesis of the simplest amino acid in the ISM. A molecular mystery in the case of the carrier of a series of transitions was resolved using observational data toward a large number of sources, confirming the identity of this important carbon-chemistry intermediate B11244 as l-C3H+ and identifying it in at least two new environments. Finally, the doubly-nitrogenated molecule carbodiimide HNCNH was identified in the ISM for the first time through maser emission features in the centimeter-wavelength regime.

In the laboratory, a TeraHertz Time-Domain Spectrometer was constructed to obtain the experimental spectra necessary to search for solid-phase species in the ISM in the THz region of the spectrum. These investigations have shown a striking dependence on large-scale, long-range (i.e. lattice) structure of the ices on the spectra they present in the THz. A database of molecular spectra has been started, and both the simplest and most abundant ice species, which have already been identified, as well as a number of more complex species, have been studied. The exquisite sensitivity of the THz spectra to both the structure and thermal history of these ices may lead to better probes of complex chemical and dynamical evolution in interstellar environments.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Physical Chemistry; Spectroscopy; Astrochemistry; Observational Astronomy; Terahertz
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Awards:Everhart Distinguished Graduate Student Lecture Series, 2014
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Blake, Geoffrey A.
Group:Astronomy Department
Thesis Committee:
  • Gray, Harry B. (chair)
  • Okumura, Mitchio
  • Marcus, Rudolph A.
  • Remijan, Anthony J.
  • Blake, Geoffrey A.
Defense Date:21 May 2014
Record Number:CaltechTHESIS:07232014-152145064
Persistent URL:
McGuire, Brett Andrew0000-0003-1254-4817
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:8598
Deposited By: Brett McGuire
Deposited On:08 Aug 2014 22:09
Last Modified:08 Nov 2023 00:16

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