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Title: Infrared Spectroscopy of the Entrance Channel Complex Formed Between the Hydroxyl Radical and Methane in Helium Nanodroplets

Abstract

Here, the entrance channel complex in the exothermic OH + CH4 → H2O + CH3 reaction has been isolated in helium nanodroplets following the sequential pick-up of the hydroxyl radical and methane. The a-type OH stretching band was probed with infrared depletion spectroscopy, revealing a spectrum qualitatively similar to that previously reported in the gas phase, but with additional substructure that is due to the different internal rotation states of methane (jCH4 = 0, 1, or 2) in the complex. We fit the spectra by assuming the rotational constants of the complex are the same for all internal rotation states; however, subband origins are found to decrease with increasing jCH4. Measurements of deuterated complexes have also been made (OD–CH4, OH–CD4, and OD–CD4), the relative linewidths of which provide information about the flow of vibrational energy in the complexes; vibrational lifetime broadening is prominent for OH–CH4 and OD–CD4, for which the excited OX stretching state has a nearby CY4 stretching fundamental (X, Y = H or D).

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2]
  1. James Madison Univ., Harrisonburg, VA (United States)
  2. Univ. of Georgia, Athens, GA (United States)
Publication Date:
Research Org.:
Univ. of Georgia, Athens, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1409064
Grant/Contract Number:  
SC0008086
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 121; Journal Issue: 40; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Raston, Paul L., Obi, Emmanuel I., and Douberly, Gary E. Infrared Spectroscopy of the Entrance Channel Complex Formed Between the Hydroxyl Radical and Methane in Helium Nanodroplets. United States: N. p., 2017. Web. https://doi.org/10.1021/acs.jpca.7b07906.
Raston, Paul L., Obi, Emmanuel I., & Douberly, Gary E. Infrared Spectroscopy of the Entrance Channel Complex Formed Between the Hydroxyl Radical and Methane in Helium Nanodroplets. United States. https://doi.org/10.1021/acs.jpca.7b07906
Raston, Paul L., Obi, Emmanuel I., and Douberly, Gary E. Fri . "Infrared Spectroscopy of the Entrance Channel Complex Formed Between the Hydroxyl Radical and Methane in Helium Nanodroplets". United States. https://doi.org/10.1021/acs.jpca.7b07906. https://www.osti.gov/servlets/purl/1409064.
@article{osti_1409064,
title = {Infrared Spectroscopy of the Entrance Channel Complex Formed Between the Hydroxyl Radical and Methane in Helium Nanodroplets},
author = {Raston, Paul L. and Obi, Emmanuel I. and Douberly, Gary E.},
abstractNote = {Here, the entrance channel complex in the exothermic OH + CH4 → H2O + CH3 reaction has been isolated in helium nanodroplets following the sequential pick-up of the hydroxyl radical and methane. The a-type OH stretching band was probed with infrared depletion spectroscopy, revealing a spectrum qualitatively similar to that previously reported in the gas phase, but with additional substructure that is due to the different internal rotation states of methane (jCH4 = 0, 1, or 2) in the complex. We fit the spectra by assuming the rotational constants of the complex are the same for all internal rotation states; however, subband origins are found to decrease with increasing jCH4. Measurements of deuterated complexes have also been made (OD–CH4, OH–CD4, and OD–CD4), the relative linewidths of which provide information about the flow of vibrational energy in the complexes; vibrational lifetime broadening is prominent for OH–CH4 and OD–CD4, for which the excited OX stretching state has a nearby CY4 stretching fundamental (X, Y = H or D).},
doi = {10.1021/acs.jpca.7b07906},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 40,
volume = 121,
place = {United States},
year = {2017},
month = {9}
}

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Works referenced in this record:

Stimulated Raman and electronic excitation of CH4–OH reactant complexes
journal, March 1999


OH vibrational activation and decay dynamics of CH4–OH entrance channel complexes
journal, April 2000

  • Wheeler, Martyn D.; Tsiouris, Maria; Lester, Marsha I.
  • The Journal of Chemical Physics, Vol. 112, Issue 15
  • DOI: 10.1063/1.481232

Activation of the CH stretching vibrations in CH[sub 4]–OH entrance channel complexes: Spectroscopy and dynamics
journal, January 2001

  • Tsiouris, Maria; Wheeler, Martyn D.; Lester, Marsha I.
  • The Journal of Chemical Physics, Vol. 114, Issue 1
  • DOI: 10.1063/1.1328747

Study of the CH3⋯H2O radical complex stabilized in helium nanodroplets
journal, January 2009

  • Rudić, Svemir; Merritt, Jeremy M.; Miller, Roger E.
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 26
  • DOI: 10.1039/b817484a

Infrared and millimeter wave spectra of the CH4–CO complex in the A internal rotation state
journal, March 2001

  • Xia, Changhong; Walker, Kaley A.; McKellar, A. R. W.
  • The Journal of Chemical Physics, Vol. 114, Issue 11
  • DOI: 10.1063/1.1349425

Rotational study of the CH 4 –CO complex: Millimeter-wave measurements and ab initio calculations
journal, October 2015

  • Surin, L. A.; Tarabukin, I. V.; Panfilov, V. A.
  • The Journal of Chemical Physics, Vol. 143, Issue 15
  • DOI: 10.1063/1.4933061

Rotational spectrum and internal rotation of a methane–HCl complex
journal, November 1990

  • Ohshima, Yasuhiro; Endo, Yasuki
  • The Journal of Chemical Physics, Vol. 93, Issue 9
  • DOI: 10.1063/1.458995

Rotational spectra and geometries of the gas-phase dimers (CH4,HF) and (CH4,HCl)
journal, September 1990


The pairwise interaction of methane and hydrogen bromide: properties of the weakly bound dimer CH4…HBr from microwave spectroscopy
journal, May 1992


The weakly bound complex CH4-H2: Observation and analysis of infrared spectra in the 350 and 1311 cm −1 regions
journal, May 1999

  • McKellar, A. R. W.; Roth, D. A.; Pak, I.
  • The Journal of Chemical Physics, Vol. 110, Issue 20
  • DOI: 10.1063/1.478872

The Ã2Σ+←X̃ 2Π transition of the NO·CH4 and NO·CD4 complexes
journal, January 2001

  • Daire, Sophia E.; Lozeille, Je´rôme; Gamblin, Stuart D.
  • Physical Chemistry Chemical Physics, Vol. 3, Issue 6
  • DOI: 10.1039/b010026i

Superfluid Helium Droplets: A Uniquely Cold Nanomatrix for Molecules and Molecular Complexes
journal, May 2004

  • Toennies, J. Peter; Vilesov, Andrey F.
  • Angewandte Chemie International Edition, Vol. 43, Issue 20
  • DOI: 10.1002/anie.200300611

Spectroscopy and dynamics in helium nanodroplets
journal, April 2006

  • Stienkemeier, Frank; Lehmann, Kevin K.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 39, Issue 8
  • DOI: 10.1088/0953-4075/39/8/R01

Infrared spectroscopy of helium nanodroplets: novel methods for physics and chemistry
journal, January 2006

  • Choi, M. Y.; Douberly, G. E.; Falconer, T. M.
  • International Reviews in Physical Chemistry, Vol. 25, Issue 1-2
  • DOI: 10.1080/01442350600625092

Infrared Action Spectroscopy and Inelastic Recoil Dynamics of the CH 4 −OD Reactant Complex
journal, August 2002

  • Tsiouris, Maria; Pollack, Ilana B.; Lester, Marsha I.
  • The Journal of Physical Chemistry A, Vol. 106, Issue 34
  • DOI: 10.1021/jp0209143

Infrared laser spectroscopy of CH3⋯HF in helium nanodroplets: The exit-channel complex of the F+CH4 reaction
journal, February 2006

  • Merritt, J. M.; Rudić, S.; Miller, R. E.
  • The Journal of Chemical Physics, Vol. 124, Issue 8
  • DOI: 10.1063/1.2168450

Dynamics of hydrogen–HF complexes in helium nanodroplets
journal, June 2003

  • Moore, David T.; Miller, Roger E.
  • The Journal of Chemical Physics, Vol. 118, Issue 21
  • DOI: 10.1063/1.1569911

Mode correlation of product pairs in the reaction OH+CD4→HOD+CD3
journal, April 2005

  • Zhang, Bailin; Shiu, Weicheng; Lin, Jim J.
  • The Journal of Chemical Physics, Vol. 122, Issue 13
  • DOI: 10.1063/1.1885466

Imaging the Reaction Dynamics of OH + CD 4 . 2. Translational Energy Dependencies
journal, October 2005

  • Zhang, Bailin; Shiu, Weicheng; Liu, Kopin
  • The Journal of Physical Chemistry A, Vol. 109, Issue 40
  • DOI: 10.1021/jp0536605

Imaging the Reaction Dynamics of OH + CD 4 . 3. Isotope Effects
journal, October 2005

  • Zhang, Bailin; Shiu, Weicheng; Liu, Kopin
  • The Journal of Physical Chemistry A, Vol. 109, Issue 40
  • DOI: 10.1021/jp053661x

Six-dimensional and seven-dimensional quantum dynamics study of the OH + CH 4 → H 2 O + CH 3 reaction
journal, October 2013

  • Song, Hongwei; Lee, Soo-Ying; Yang, Minghui
  • The Journal of Chemical Physics, Vol. 139, Issue 15
  • DOI: 10.1063/1.4825100

Effects of reactant rotation on the dynamics of the OH + CH 4 → H 2 O + CH 3 reaction: A six-dimensional study
journal, February 2014

  • Song, Hongwei; Li, Jun; Jiang, Bin
  • The Journal of Chemical Physics, Vol. 140, Issue 8
  • DOI: 10.1063/1.4866426

QCT dynamics study of the reaction of hydroxyl radical and methane using a new ab initio fitted full-dimensional analytical potential energy surface
journal, January 2015

  • Espinosa-Garcia, Joaquin; Corchado, Jose C.
  • Theoretical Chemistry Accounts, Vol. 134, Issue 2
  • DOI: 10.1007/s00214-014-1607-1

Reflected Shock Tube Studies of High-Temperature Rate Constants for OH + CH 4 → CH 3 + H 2 O and CH 3 + NO 2 → CH 3 O + NO
journal, March 2005

  • Srinivasan, N. K.; Su, M. -C.; Sutherland, J. W.
  • The Journal of Physical Chemistry A, Vol. 109, Issue 9
  • DOI: 10.1021/jp040679j

Anomalous Λ-Doubling in the Infrared Spectrum of the Hydroxyl Radical in Helium Nanodroplets
journal, February 2013

  • Raston, Paul L.; Liang, Tao; Douberly, Gary E.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 34
  • DOI: 10.1021/jp312335q

Observation of the Q (3/2) Λ-doublet transitions for X 2 Π 3/2 OD in helium nanodroplets
journal, June 2013


Automation of an “Aculight” continuous-wave optical parametric oscillator
journal, January 2013

  • Morrison, Alexander M.; Liang, Tao; Douberly, Gary E.
  • Review of Scientific Instruments, Vol. 84, Issue 1
  • DOI: 10.1063/1.4776179

Infrared Spectroscopy of (HCl) m (H 2 O) n Clusters in Helium Nanodroplets: Definitive Assignments in the HCl Stretch Region
journal, August 2010

  • Morrison, Alexander M.; Flynn, Steven D.; Liang, Tao
  • The Journal of Physical Chemistry A, Vol. 114, Issue 31
  • DOI: 10.1021/jp104545j

Infrared spectroscopy of HOOO and DOOO in 4 He nanodroplets
journal, November 2012

  • Raston, Paul L.; Liang, Tao; Douberly, Gary E.
  • The Journal of Chemical Physics, Vol. 137, Issue 18
  • DOI: 10.1063/1.4764298

Helium nanodroplet isolation rovibrational spectroscopy: Methods and recent results
journal, January 2001

  • Callegari, Carlo; Lehmann, Kevin K.; Schmied, Roman
  • The Journal of Chemical Physics, Vol. 115, Issue 22
  • DOI: 10.1063/1.1418746

Infrared rovibrational spectroscopy of OH–C 2 H 2 in 4 He nanodroplets: Parity splitting due to partially quenched electronic angular momentum
journal, April 2015

  • Douberly, Gary E.; Raston, Paul L.; Liang, Tao
  • The Journal of Chemical Physics, Vol. 142, Issue 13
  • DOI: 10.1063/1.4916394

Mid-infrared signatures of hydroxyl containing water clusters: Infrared laser Stark spectroscopy of OH–H 2 O and OH(D 2 O) n ( n = 1-3)
journal, October 2015

  • Hernandez, Federico J.; Brice, Joseph T.; Leavitt, Christopher M.
  • The Journal of Chemical Physics, Vol. 143, Issue 16
  • DOI: 10.1063/1.4933432

Infrared Stark and Zeeman spectroscopy of OH–CO: The entrance channel complex along the OH + CO → trans-HOCO reaction pathway
journal, September 2016

  • Brice, Joseph T.; Liang, Tao; Raston, Paul L.
  • The Journal of Chemical Physics, Vol. 145, Issue 12
  • DOI: 10.1063/1.4963226

PGOPHER: A program for simulating rotational, vibrational and electronic spectra
journal, January 2017


Solvent mediated vibrational relaxation: Superfluid helium droplet spectroscopy of HCN dimer
journal, August 1999

  • Nauta, K.; Miller, R. E.
  • The Journal of Chemical Physics, Vol. 111, Issue 8
  • DOI: 10.1063/1.479627

The hydrogen fluoride dimer in liquid helium: A prototype system for studying solvent effects on hydrogen bonding
journal, December 2000

  • Nauta, K.; Miller, R. E.
  • The Journal of Chemical Physics, Vol. 113, Issue 22
  • DOI: 10.1063/1.1289824

Infrared Action Spectroscopy and Dissociation Dynamics of the HOOO Radical
journal, November 2007

  • Derro, Erika L.; Murray, Craig; Sechler, Timothy D.
  • The Journal of Physical Chemistry A, Vol. 111, Issue 45
  • DOI: 10.1021/jp0760915

    Works referencing / citing this record:

    Infrared spectroscopy in superfluid helium droplets
    journal, December 2018


    Rotational energy relaxation quantum dynamics of a diatomic molecule in a superfluid helium nanodroplet and study of the hydrogen isotopes case
    journal, January 2019

    • Blancafort-Jorquera, Miquel; Vilà, Arnau; González, Miguel
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 37
    • DOI: 10.1039/c9cp00952c