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Title: Broadband multi-resonant strong field coherence breaking as a tool for single isomer microwave spectroscopy

Abstract

Using standard hardware available in chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy, an experimental method is introduced to selectively extract from the microwave spectrum of an otherwise complicated multicomponent mixture a set of transitions due to a single component, thereby speeding spectral assignment. The method operates the broadband chirped-pulse used to excite the sample in the strong-field limit through a combination of high power and control of the sweep rate. A procedure is introduced that leads to selection of three transition frequencies that can be incorporated as a set of resonant sequential single-frequency microwave pulses that follow broadband chirped-pulse excitation, resulting in a reduction in the coherent signal from a set of transitions ascribable to the component of interest. The difference in the CP-FTMW spectrum with and without this set of multi-resonant single-frequency pulses produces a set of transitions that can confidently be assigned to a single component of the mixture, aiding the analysis of its spectrum. In conclusion, the scheme is applied to (i) selectively extract the spectrum of one of five singly 13C-subsituted isotopologues of benzonitrile in natural abundance, (ii) obtain the microwave spectra of the two structural isomers (E)- and (Z)-phenylvinylnitrile, and (iii) obtain conformer-specific microwave spectra ofmore » methylbutyrate.« less

Authors:
 [1];  [1];  [1]; ORCiD logo [1]
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  1. Purdue Univ., West Lafayette, IN (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Purdue Univ., West Lafayette, IN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1467887
Alternate Identifier(s):
OSTI ID: 1325601
Grant/Contract Number:  
FG02-96ER14656; PRF #55152-ND6
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 11; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Hernandez-Castillo, A. O., Abeysekera, Chamara, Hays, Brian M., and Zwier, Timothy S. Broadband multi-resonant strong field coherence breaking as a tool for single isomer microwave spectroscopy. United States: N. p., 2016. Web. doi:10.1063/1.4962505.
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Hernandez-Castillo, A. O., Abeysekera, Chamara, Hays, Brian M., & Zwier, Timothy S. Broadband multi-resonant strong field coherence breaking as a tool for single isomer microwave spectroscopy. United States. https://doi.org/10.1063/1.4962505
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Hernandez-Castillo, A. O., Abeysekera, Chamara, Hays, Brian M., and Zwier, Timothy S. Tue . "Broadband multi-resonant strong field coherence breaking as a tool for single isomer microwave spectroscopy". United States. https://doi.org/10.1063/1.4962505. https://www.osti.gov/servlets/purl/1467887.
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@article{osti_1467887,
title = {Broadband multi-resonant strong field coherence breaking as a tool for single isomer microwave spectroscopy},
author = {Hernandez-Castillo, A. O. and Abeysekera, Chamara and Hays, Brian M. and Zwier, Timothy S.},
abstractNote = {Using standard hardware available in chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy, an experimental method is introduced to selectively extract from the microwave spectrum of an otherwise complicated multicomponent mixture a set of transitions due to a single component, thereby speeding spectral assignment. The method operates the broadband chirped-pulse used to excite the sample in the strong-field limit through a combination of high power and control of the sweep rate. A procedure is introduced that leads to selection of three transition frequencies that can be incorporated as a set of resonant sequential single-frequency microwave pulses that follow broadband chirped-pulse excitation, resulting in a reduction in the coherent signal from a set of transitions ascribable to the component of interest. The difference in the CP-FTMW spectrum with and without this set of multi-resonant single-frequency pulses produces a set of transitions that can confidently be assigned to a single component of the mixture, aiding the analysis of its spectrum. In conclusion, the scheme is applied to (i) selectively extract the spectrum of one of five singly 13C-subsituted isotopologues of benzonitrile in natural abundance, (ii) obtain the microwave spectra of the two structural isomers (E)- and (Z)-phenylvinylnitrile, and (iii) obtain conformer-specific microwave spectra of methylbutyrate.},
doi = {10.1063/1.4962505},
journal = {Journal of Chemical Physics},
number = 11,
volume = 145,
place = {United States},
year = {Tue Sep 20 00:00:00 EDT 2016},
month = {Tue Sep 20 00:00:00 EDT 2016}
}
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https://doi.org/10.1063/1.4962505
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    Works referencing / citing this record:

    Broadband rotational spectroscopy of trans 3-pentenenitrile and 4-pentenenitrile
    journal, January 2019

    • Mishra, Piyush; Fritz, Sean M.; Hays, Brian M.
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 42
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    Automated assignment of rotational spectra using artificial neural networks
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    Multiplexed characterization of complex gas-phase mixtures combining chirped-pulse Fourier transform microwave spectroscopy and VUV photoionization time-of-flight mass spectrometry
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    • Fritz, Sean M.; Hays, Brian M.; Hernandez-Castillo, Alicia O.
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    Propagating molecular rotational coherences through single-frequency pulses in the strong field regime
    journal, August 2019

    • Hernandez-Castillo, A. O.; Abeysekera, Chamara; Robicheaux, F.
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    • DOI: 10.1063/1.5099049

    Strong-field coherence breaking as a tool for identifying methyl rotor states in microwave spectra: 2-hexanone
    journal, July 2019

    • Fritz, Sean M.; Mishra, Piyush; Zwier, Timothy S.
    • The Journal of Chemical Physics, Vol. 151, Issue 4
    • DOI: 10.1063/1.5109656

    Automated Assignment of Rotational Spectra Using Artificial Neural Networks
    conference, June 2018

    • Zaleski, Daniel; Prozument, Kirill
    • Proceedings of the 73rd International Symposium on Molecular Spectroscopy
    • DOI: 10.15278/isms.2018.th01
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