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Title: Infrared laser spectroscopy of the n-propyl and i-propyl radicals: Stretch-bend Fermi coupling in the alkyl CH stretch region

Abstract

The n-propyl and i-propyl radicals were generated in the gas phase via pyrolysis of n-butyl nitrite [CH3(CH2)3ONO] and i-butyl nitrite [(CH3)2CHCH2ONO], respectively. Nascent radicals were promptly solvated by a beam of He nanodroplets, and the infrared spectra of the radicals were recorded in the CH stretching region. Several previously unreported bands are observed between 2800 and 3150 cm–1. The CH stretching modes observed above 3000 cm–1 are in excellent agreement with CCSD(T) anharmonic frequencies computed using second-order vibrational perturbation theory. However, between 2800 and 3000 cm–1, the spectra of n- and i-propyl radicals become congested and difficult to assign due to the presence of multiple anharmonic resonance polyads. To model the spectrally congested region, Fermi and Darling-Dennison resonances are treated explicitly using “dressed” Hamiltonians and CCSD(T) quartic force fields in the normal mode representation, and the agreement with experiment is less than satisfactory. Computations employing local mode effective Hamiltonians reveal the origin of the spectral congestion to be strong coupling between the high frequency CH stretching modes and the lower frequency CHn bending/scissoring motions. The most significant coupling is between stretches and bends localized on the same CH2/CH3 group. As a result, spectral simulations using the local mode approach aremore » in excellent agreement with experiment.« less

Authors:
 [1]; ORCiD logo [2];  [1]; ORCiD logo [1];  [1];  [1]; ORCiD logo [2]
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  1. Univ. of Georgia, Athens, GA (United States)
  2. Univ. of Wisconsin-Madison, Madison, WI (United States)
Publication Date:
Research Org.:
Univ. of Georgia, Athens, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1409063
Alternate Identifier(s):
OSTI ID: 1335712
Grant/Contract Number:  
SC0008086; AC02-05CH11231; FG02-12ER16298; FG02-97ER14748
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 22; 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

Citation Formats

Franke, Peter R., Tabor, Daniel P., Moradi, Christopher P., Douberly, Gary E., Agarwal, Jay, Schaefer, III, Henry F., and Sibert, Edwin L. Infrared laser spectroscopy of the n-propyl and i-propyl radicals: Stretch-bend Fermi coupling in the alkyl CH stretch region. United States: N. p., 2016. Web. doi:10.1063/1.4971239.
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Franke, Peter R., Tabor, Daniel P., Moradi, Christopher P., Douberly, Gary E., Agarwal, Jay, Schaefer, III, Henry F., & Sibert, Edwin L. Infrared laser spectroscopy of the n-propyl and i-propyl radicals: Stretch-bend Fermi coupling in the alkyl CH stretch region. United States. https://doi.org/10.1063/1.4971239
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Franke, Peter R., Tabor, Daniel P., Moradi, Christopher P., Douberly, Gary E., Agarwal, Jay, Schaefer, III, Henry F., and Sibert, Edwin L. Tue . "Infrared laser spectroscopy of the n-propyl and i-propyl radicals: Stretch-bend Fermi coupling in the alkyl CH stretch region". United States. https://doi.org/10.1063/1.4971239. https://www.osti.gov/servlets/purl/1409063.
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@article{osti_1409063,
title = {Infrared laser spectroscopy of the n-propyl and i-propyl radicals: Stretch-bend Fermi coupling in the alkyl CH stretch region},
author = {Franke, Peter R. and Tabor, Daniel P. and Moradi, Christopher P. and Douberly, Gary E. and Agarwal, Jay and Schaefer, III, Henry F. and Sibert, Edwin L.},
abstractNote = {The n-propyl and i-propyl radicals were generated in the gas phase via pyrolysis of n-butyl nitrite [CH3(CH2)3ONO] and i-butyl nitrite [(CH3)2CHCH2ONO], respectively. Nascent radicals were promptly solvated by a beam of He nanodroplets, and the infrared spectra of the radicals were recorded in the CH stretching region. Several previously unreported bands are observed between 2800 and 3150 cm–1. The CH stretching modes observed above 3000 cm–1 are in excellent agreement with CCSD(T) anharmonic frequencies computed using second-order vibrational perturbation theory. However, between 2800 and 3000 cm–1, the spectra of n- and i-propyl radicals become congested and difficult to assign due to the presence of multiple anharmonic resonance polyads. To model the spectrally congested region, Fermi and Darling-Dennison resonances are treated explicitly using “dressed” Hamiltonians and CCSD(T) quartic force fields in the normal mode representation, and the agreement with experiment is less than satisfactory. Computations employing local mode effective Hamiltonians reveal the origin of the spectral congestion to be strong coupling between the high frequency CH stretching modes and the lower frequency CHn bending/scissoring motions. The most significant coupling is between stretches and bends localized on the same CH2/CH3 group. As a result, spectral simulations using the local mode approach are in excellent agreement with experiment.},
doi = {10.1063/1.4971239},
journal = {Journal of Chemical Physics},
number = 22,
volume = 145,
place = {United States},
year = {Tue Dec 13 00:00:00 EST 2016},
month = {Tue Dec 13 00:00:00 EST 2016}
}
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