skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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]
  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. https://doi.org/10.1063/1.5109656.
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
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.
@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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Infrared spectrum, ab initio calculations, barriers to internal rotation and structural parameters for methyl nitrite
journal, May 1990

  • Van der Veken, B. J.; Maas, R.; Guirgis, G. A.
  • The Journal of Physical Chemistry, Vol. 94, Issue 10
  • DOI: 10.1021/j100373a028

The low internal rotation barriers of halogenated toluenes: Rotational spectrum of 2,4-difluorotoluene
journal, February 2018

  • Nair, K. P. Rajappan; Herbers, Sven; Obenchain, Daniel A.
  • Journal of Molecular Spectroscopy, Vol. 344
  • DOI: 10.1016/j.jms.2017.10.003

A high-temperature study of 2-pentanone oxidation: experiment and kinetic modeling
journal, January 2019

  • Pieper, Julia; Hemken, Christian; Büttgen, Rene
  • Proceedings of the Combustion Institute, Vol. 37, Issue 2
  • DOI: 10.1016/j.proci.2018.05.039

Ultraviolet spectroscopy of fundamental lignin subunits: Guaiacol, 4-methylguaiacol, syringol, and 4-methylsyringol
journal, October 2013

  • Dean, Jacob C.; Navotnaya, Polina; Parobek, Alexander P.
  • The Journal of Chemical Physics, Vol. 139, Issue 14
  • DOI: 10.1063/1.4824019

Room temperature chirped-pulse Fourier transform microwave spectroscopy of anisole
journal, December 2011

  • Reinhold, B.; Finneran, I. A.; Shipman, S. T.
  • Journal of Molecular Spectroscopy, Vol. 270, Issue 2
  • DOI: 10.1016/j.jms.2011.10.002

Multiplexed characterization of complex gas-phase mixtures combining chirped-pulse Fourier transform microwave spectroscopy and VUV photoionization time-of-flight mass spectrometry
journal, September 2018

  • Fritz, Sean M.; Hays, Brian M.; Hernandez-Castillo, Alicia O.
  • Review of Scientific Instruments, Vol. 89, Issue 9
  • DOI: 10.1063/1.5046085

Semiempirical hybrid density functional with perturbative second-order correlation
journal, January 2006

  • Grimme, Stefan
  • The Journal of Chemical Physics, Vol. 124, Issue 3
  • DOI: 10.1063/1.2148954

Acetyl Methyl Torsion in Pentan-2-one As Observed by Microwave Spectroscopy
journal, August 2018

  • Andresen, Maike; Kleiner, Isabelle; Schwell, Martin
  • The Journal of Physical Chemistry A, Vol. 122, Issue 35
  • DOI: 10.1021/acs.jpca.8b06183

Theoretical and spectroscopic study of asymmetric methyl rotor dynamics in gaseous partially deuterated nitromethanes
journal, April 1993

  • Gorse, Dominique; Cavagnat, Dominique; Pesquer, Michel
  • The Journal of Physical Chemistry, Vol. 97, Issue 17
  • DOI: 10.1021/j100119a005

Rotational spectroscopy of the methyl glycidate–water complex: conformation and water and methyl rotor tunnelling motions
journal, January 2017

  • Gall, Jason T. A.; Thomas, Javix; Xie, Fan
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 43
  • DOI: 10.1039/c7cp05464e

14 N Nuclear Quadrupole Coupling and Methyl Internal Rotation in N - tert -Butylacetamide As Observed by Microwave Spectroscopy
journal, June 2016

  • Kannengießer, Raphaela; Stahl, Wolfgang; Nguyen, Ha Vinh Lam
  • The Journal of Physical Chemistry A, Vol. 120, Issue 23
  • DOI: 10.1021/acs.jpca.6b02111

The effects of two internal rotations in the microwave spectrum of ethyl methyl ketone
journal, June 2014

  • Nguyen, Ha Vinh Lam; Van, Vinh; Stahl, Wolfgang
  • The Journal of Chemical Physics, Vol. 140, Issue 21
  • DOI: 10.1063/1.4878412

The microwave spectrum of allyl acetone
journal, June 2015

  • Tulimat, Layla; Mouhib, Halima; Kleiner, Isabelle
  • Journal of Molecular Spectroscopy, Vol. 312
  • DOI: 10.1016/j.jms.2015.03.006

Conformational Properties of cis - and trans - N -Cyclopropylformamide Studied by Microwave Spectroscopy and Quantum Chemical Calculations
journal, March 2015

  • Samdal, Svein; Møllendal, Harald; Guillemin, Jean-Claude
  • The Journal of Physical Chemistry A, Vol. 119, Issue 14
  • DOI: 10.1021/acs.jpca.5b00542

The fitting and prediction of vibration-rotation spectra with spin interactions
journal, August 1991


Communication: Spectroscopic characterization of an alkyl substituted Criegee intermediate syn -CH 3 CHOO through pure rotational transitions
journal, January 2014

  • Nakajima, Masakazu; Endo, Yasuki
  • The Journal of Chemical Physics, Vol. 140, Issue 1
  • DOI: 10.1063/1.4861494

Broadband Microwave Spectroscopy of 2-Furanyloxy Radical: Primary Pyrolysis Product of the Second-Generation Biofuel 2-Methoxyfuran
journal, July 2018

  • Abeysekera, Chamara; Hernandez-Castillo, A. O.; Stanton, John F.
  • The Journal of Physical Chemistry A, Vol. 122, Issue 34
  • DOI: 10.1021/acs.jpca.8b05102

Torsional frequencies in the far infrared—I
journal, January 1961


The microwave spectroscopy study of 1,2-dimethoxyethane
journal, July 2017

  • Li, Weixing; Vigorito, Annalisa; Calabrese, Camilla
  • Journal of Molecular Spectroscopy, Vol. 337
  • DOI: 10.1016/j.jms.2017.02.015

Structural Information from Methyl Internal Rotation Spectroscopy
journal, October 1997


Methyl Internal Rotation in the Microwave Spectrum of o -Methyl Anisole
journal, May 2017


A comprehensive experimental and kinetic modeling study of butanone
journal, June 2016


Broadband multi-resonant strong field coherence breaking as a tool for single isomer microwave spectroscopy
journal, September 2016

  • Hernandez-Castillo, A. O.; Abeysekera, Chamara; Hays, Brian M.
  • The Journal of Chemical Physics, Vol. 145, Issue 11
  • DOI: 10.1063/1.4962505

Structure and rotational dynamics of methyl propionate studied by microwave spectroscopy
journal, September 2012


Origin of Methyl Internal Rotation Barriers
journal, December 1999

  • Goodman, Lionel; Pophristic, Vojislava; Weinhold, Frank
  • Accounts of Chemical Research, Vol. 32, Issue 12
  • DOI: 10.1021/ar990069f

Internal Rotation and Microwave Spectroscopy
journal, October 1959


Performance and emissions analysis on using acetone–gasoline fuel blends in spark-ignition engine
journal, September 2016


Conformational preferences and internal rotation of methyl butyrate by microwave spectroscopy
journal, July 2017

  • Hernandez-Castillo, Alicia O.; Abeysekera, Chamara; Hays, Brian M.
  • Journal of Molecular Spectroscopy, Vol. 337
  • DOI: 10.1016/j.jms.2017.03.016

The effects of nitrogen inversion tunneling, methyl internal rotation, and 14 N quadrupole coupling observed in the rotational spectrum of diethyl amine
journal, July 2011

  • Vinh Lam Nguyen, Ha; Stahl, Wolfgang
  • The Journal of Chemical Physics, Vol. 135, Issue 2
  • DOI: 10.1063/1.3607992

A broadband Fourier transform microwave spectrometer based on chirped pulse excitation
journal, May 2008

  • Brown, Gordon G.; Dian, Brian C.; Douglass, Kevin O.
  • Review of Scientific Instruments, Vol. 79, Issue 5
  • DOI: 10.1063/1.2919120

The Microwave Spectrum of trans-2,3-Dimethyloxirane in Torsional Excited States
journal, January 1996

  • Hartwig, H.; Dreizler, H.
  • Zeitschrift für Naturforschung A, Vol. 51, Issue 8
  • DOI: 10.1515/zna-1996-0807

Conformer-specific microwave spectroscopy of 3-phenylpropionitrile by strong field coherence breaking
journal, July 2018

  • Fritz, Sean M.; Hernandez-Castillo, A. O.; Abeysekera, Chamara
  • Journal of Molecular Spectroscopy, Vol. 349
  • DOI: 10.1016/j.jms.2018.03.011