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Title: Strong-field coherence breaking as a tool for identifying methyl rotor states in microwave spectra: 2-hexanone

Abstract

The rotational spectrum of 2-hexanone was recorded over the 8–18 GHz region using a chirped pulse Fourier transform microwave spectrometer. Strong field coherence breaking (SFCB) was utilized to selectively modulate the intensities of rotational transitions belonging to the two lowest energy conformers of 2-hexanone, aiding the assignment. In addition, the SFCB method was applied for the first time to selectively identify rotational transitions built off the two lowest energy hindered methyl rotor states of each conformer, 0a1 and 1e. Since these two states have rotational energy levels with different nuclear spin symmetries, their intensities could be selectively modulated by the resonant monochromatic pulses used in the SFCB method. Here, the difference spectra, final fit, and structural parameters are discussed for the three assigned conformers of 2-hexanone.

Authors:
 [1];  [1]; ORCiD logo [1]
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  1. Purdue Univ., West Lafayette, IN (United States)
Publication Date:
Research Org.:
Purdue Univ., West Lafayette, IN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1610306
Grant/Contract Number:  
FG02-96ER14656
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 4; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; chemistry; physics; isomerism; Fourier transform spectroscopy; potential energy surfaces; rotational dynamics; microwave spectroscopy; chemical compounds; quantum coherence; rotational spectra; Becke; three-parameter; Lee-Yang-Parr

Citation Formats

Fritz, Sean M., Mishra, Piyush, and Zwier, Timothy S. Strong-field coherence breaking as a tool for identifying methyl rotor states in microwave spectra: 2-hexanone. United States: N. p., 2019. Web. doi:10.1063/1.5109656.
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Fritz, Sean M., Mishra, Piyush, & Zwier, Timothy S. Strong-field coherence breaking as a tool for identifying methyl rotor states in microwave spectra: 2-hexanone. United States. https://doi.org/10.1063/1.5109656
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Fritz, Sean M., Mishra, Piyush, and Zwier, Timothy S. Wed . "Strong-field coherence breaking as a tool for identifying methyl rotor states in microwave spectra: 2-hexanone". United States. https://doi.org/10.1063/1.5109656. https://www.osti.gov/servlets/purl/1610306.
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@article{osti_1610306,
title = {Strong-field coherence breaking as a tool for identifying methyl rotor states in microwave spectra: 2-hexanone},
author = {Fritz, Sean M. and Mishra, Piyush and Zwier, Timothy S.},
abstractNote = {The rotational spectrum of 2-hexanone was recorded over the 8–18 GHz region using a chirped pulse Fourier transform microwave spectrometer. Strong field coherence breaking (SFCB) was utilized to selectively modulate the intensities of rotational transitions belonging to the two lowest energy conformers of 2-hexanone, aiding the assignment. In addition, the SFCB method was applied for the first time to selectively identify rotational transitions built off the two lowest energy hindered methyl rotor states of each conformer, 0a1 and 1e. Since these two states have rotational energy levels with different nuclear spin symmetries, their intensities could be selectively modulated by the resonant monochromatic pulses used in the SFCB method. Here, the difference spectra, final fit, and structural parameters are discussed for the three assigned conformers of 2-hexanone.},
doi = {10.1063/1.5109656},
journal = {Journal of Chemical Physics},
number = 4,
volume = 151,
place = {United States},
year = {2019},
month = {7}
}
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Journal Article:
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https://doi.org/10.1063/1.5109656
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Figures / Tables:

FIG. 1 FIG. 1: Top, down, and side views of the four lowest energy conformers of 2-hexanone predicted at the B3LYP-D3BJ/Def2TZVP level of theory.
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