Doctoral Dissertations

Keywords and Phrases

Chirality; cp-ftmw; microwave spectroscopy; microwave three-wave mixing; rotational spectroscopy; structure determination

Abstract

"Rotational spectroscopy has established itself as a reliable gas-phase spectroscopic technique for the structural determination of molecules. This reliability has stemmed from both advancements in microwave technology and a willingness from the community to push the boundaries of the field. In this dissertation, the boundaries are tested in both how well the technique can determine the structure of molecules exhibiting large amplitude motion and through chirality determination. The first half of this dissertation explores the use of deep averaging to determine the structure of silicon containing molecules in collaboration with Dr. Guirgis from the College of Charleston. For each of these molecules, the ground electronic and vibrational state, pure rotational spectrum was analyzed via CP-FTMW spectroscopy. The parent species and singly substituted isotopologues for each molecule were observed in natural abundance and are reported, which allowed for rs structures to be generated. The second half of this dissertation explores the use of microwave three-wave mixing (M3WM) spectroscopy to determine a molecule’s chirality and measure enantiomeric excess. Building off the previous works of Schnell, Patterson, and Pate, a M3WM spectrometer was constructed and demonstrated at Missouri University of Science and Technology for the use of chirality determination. The first molecule studied with this instrument was carvone, whose traditional rotational spectrum is denominated by internal rotation splittings from two non-equivalent methyl rotors. This M3WM experiment marked the first time a M3WM experiment was completely operable in the 6-18 GHz region of the electromagnetic spectrum and also demonstrated the first use of synchronized arbitrary waveform generators for orthogonal pulse generation. Within this work, the design, construction, and demonstration of the M3WM instrument’s capabilities using the enantiomers of carvone will be discussed along with the updated spectrum analysis of carvone"-- Abstract, p. iv

Advisor(s)

Grubbs, Garry S.

Committee Member(s)

Woelk, Klaus
Winiarz, Jeffrey G.
Dawes, Richard
Donnell, Kristen M.

Department(s)

Chemistry

Degree Name

Ph. D. in Chemistry

Publisher

Missouri University of Science and Technology

Publication Date

Spring 2024

Pagination

xvii, 607 pages

Note about bibliography

Includes_bibliographical_references_(pages 86, 114, 130, 145, 185 and 604-606)

Rights

© 2023 Nicole Taylor Moon, All rights reserved

Document Type

Dissertation - Open Access

File Type

text

Language

English

Thesis Number

T 12340

Electronic OCLC #

1427207823

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Chemistry Commons

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