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Chirped Pulse Rotational Spectroscopy of Small Molecule Clusters


Dutton, Sarah Emily (2023) Chirped Pulse Rotational Spectroscopy of Small Molecule Clusters. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/dxsp-c265.


Despite the ubiquity of water and alcohol mixtures in every realm of science, the hydrogen bond network governing the unique properties of these mixtures is still under investigation. To aid in the determination of hydrogen bond energetics and dynamics in alcohol and water mixtures, herein a ground up approach studying small alcohol:water clusters is presented. Novel instrumentation for chirped pulse Fourier-transform microwave spectroscopy was developed, and subsequently benchmarked against the detection and characterization of ethanol and water trimers. From there, cluster size was gradually increased, first studying ethanol and water tetramers, then switching to methanol for larger cluster studies of pentamers and hexamers. Throughout this thesis, the over-arching questions as to microaggregation in clusters and trends in geometry and relative energy ordering were investigated, and evidence supporting the facile mixing of small alcohols and water is presented at the few-molecule cluster scale. In the final studies of methanol and water hexamers, the first `3-dimensional' bonding motifs of methanol and water clusters are observed, marking the transition from the planar conformers of small clusters to the complex and higher cooperativity bonding patterns in larger clusters and in bulk mixtures.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Rotational spectroscopy, Microwave spectroscopy, chirped pulse, clusters
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Blake, Geoffrey A.
Thesis Committee:
  • Wei, Lu (chair)
  • Cushing, Scott K.
  • Fu, Gregory C.
  • Blake, Geoffrey A.
Defense Date:23 March 2023
Funding AgencyGrant Number
NSF Graduate Research Fellowship ProgramDGE‐1745301
Record Number:CaltechTHESIS:04172023-221653165
Persistent URL:
Related URLs:
URLURL TypeDescription adapted for Chapter 2 adapted for Chapter 3
Dutton, Sarah Emily0000-0002-9587-5971
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:15141
Deposited By: Sarah Dutton
Deposited On:08 May 2023 23:54
Last Modified:08 Nov 2023 00:16

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