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

Raston, Paul L.; Obi, Emmanuel I.; Douberly, Gary E.

doi:10.1021/acs.jpca.7b07906

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

Journal Article · 22 September 2017 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI: https://doi.org/10.1021/acs.jpca.7b07906 · OSTI ID:1409064

^[1]; Obi, Emmanuel I. ^[2];

^[2]

James Madison Univ., Harrisonburg, VA (United States)
Univ. of Georgia, Athens, GA (United States)

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 (j_CH₄ = 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 j_CH₄. 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).

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Research Organization:: Univ. of Georgia, Athens, GA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0008086

OSTI ID:: 1409064

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 121, Issue 40; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (39)

Preindustrial to present-day changes in tropospheric hydroxyl radical and methane lifetime from the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP) Naik, V.; Voulgarakis, A.; Fiore, A. M. Atmospheric Chemistry and Physics, Vol. 13, Issue 10 https://doi.org/10.5194/acp-13-5277-2013	journal	January 2013
Importance of tunneling in H-abstraction reactions by OH radicals: The case of CH ₄ + OH studied through isotope-substituted analogs Lamberts, T.; Fedoseev, G.; Kästner, J. Astronomy & Astrophysics, Vol. 599 https://doi.org/10.1051/0004-6361/201629845	journal	March 2017
Stimulated Raman and electronic excitation of CH4–OH reactant complexes Tsiouris, Maria; Wheeler, Martyn D.; Lester, Marsha I. Chemical Physics Letters, Vol. 302, Issue 1-2 https://doi.org/10.1016/S0009-2614(99)00075-5	journal	March 1999
OH vibrational activation and decay dynamics of CH4–OH entrance channel complexes Wheeler, Martyn D.; Tsiouris, Maria; Lester, Marsha I. The Journal of Chemical Physics, Vol. 112, Issue 15 https://doi.org/10.1063/1.481232	journal	April 2000
Activation of the CH stretching vibrations in CH[sub 4]–OH entrance channel complexes: Spectroscopy and dynamics Tsiouris, Maria; Wheeler, Martyn D.; Lester, Marsha I. The Journal of Chemical Physics, Vol. 114, Issue 1 https://doi.org/10.1063/1.1328747	journal	January 2001
Study of the CH3⋯H2O radical complex stabilized in helium nanodroplets Rudić, Svemir; Merritt, Jeremy M.; Miller, Roger E. Physical Chemistry Chemical Physics, Vol. 11, Issue 26 https://doi.org/10.1039/b817484a	journal	January 2009
Infrared and millimeter wave spectra of the CH4–CO complex in the A internal rotation state Xia, Changhong; Walker, Kaley A.; McKellar, A. R. W. The Journal of Chemical Physics, Vol. 114, Issue 11 https://doi.org/10.1063/1.1349425	journal	March 2001
Rotational study of the CH ₄ –CO complex: Millimeter-wave measurements and ab initio calculations Surin, L. A.; Tarabukin, I. V.; Panfilov, V. A. The Journal of Chemical Physics, Vol. 143, Issue 15 https://doi.org/10.1063/1.4933061	journal	October 2015
Rotational spectrum and internal rotation of a methane–HCl complex Ohshima, Yasuhiro; Endo, Yasuki The Journal of Chemical Physics, Vol. 93, Issue 9 https://doi.org/10.1063/1.458995	journal	November 1990
Rotational spectra and geometries of the gas-phase dimers (CH4,HF) and (CH4,HCl) Legon, A. C.; Roberts, B. P.; Wallwork, A. L. Chemical Physics Letters, Vol. 173, Issue 1 https://doi.org/10.1016/0009-2614(90)85312-Z	journal	September 1990
The pairwise interaction of methane and hydrogen bromide: properties of the weakly bound dimer CH4…HBr from microwave spectroscopy Atkins, M. J.; Legon, A. C.; Wallwork, A. L. Chemical Physics Letters, Vol. 192, Issue 4 https://doi.org/10.1016/0009-2614(92)85484-R	journal	May 1992
The weakly bound complex CH4-H2: Observation and analysis of infrared spectra in the 350 and 1311 cm ⁻¹ regions McKellar, A. R. W.; Roth, D. A.; Pak, I. The Journal of Chemical Physics, Vol. 110, Issue 20 https://doi.org/10.1063/1.478872	journal	May 1999
The Ã2Σ+←X̃ 2Π transition of the NO·CH4 and NO·CD4 complexes Daire, Sophia E.; Lozeille, Je´rôme; Gamblin, Stuart D. Physical Chemistry Chemical Physics, Vol. 3, Issue 6 https://doi.org/10.1039/b010026i	journal	January 2001
Superfluid Helium Droplets: A Uniquely Cold Nanomatrix for Molecules and Molecular Complexes Toennies, J. Peter; Vilesov, Andrey F. Angewandte Chemie International Edition, Vol. 43, Issue 20 https://doi.org/10.1002/anie.200300611	journal	May 2004
Infrared spectroscopy of helium nanodroplets: novel methods for physics and chemistry Choi, M. Y.; Douberly, G. E.; Falconer, T. M. International Reviews in Physical Chemistry, Vol. 25, Issue 1-2 https://doi.org/10.1080/01442350600625092	journal	January 2006
Infrared Action Spectroscopy and Inelastic Recoil Dynamics of the CH ₄ −OD Reactant Complex Tsiouris, Maria; Pollack, Ilana B.; Lester, Marsha I. The Journal of Physical Chemistry A, Vol. 106, Issue 34 https://doi.org/10.1021/jp0209143	journal	August 2002
Infrared laser spectroscopy of CH3⋯HF in helium nanodroplets: The exit-channel complex of the F+CH4 reaction Merritt, J. M.; Rudić, S.; Miller, R. E. The Journal of Chemical Physics, Vol. 124, Issue 8 https://doi.org/10.1063/1.2168450	journal	February 2006
Dynamics of hydrogen–HF complexes in helium nanodroplets Moore, David T.; Miller, Roger E. The Journal of Chemical Physics, Vol. 118, Issue 21 https://doi.org/10.1063/1.1569911	journal	June 2003
Mode correlation of product pairs in the reaction OH+CD4→HOD+CD3 Zhang, Bailin; Shiu, Weicheng; Lin, Jim J. The Journal of Chemical Physics, Vol. 122, Issue 13 https://doi.org/10.1063/1.1885466	journal	April 2005
Imaging the Reaction Dynamics of OH + CD ₄ . 2. Translational Energy Dependencies Zhang, Bailin; Shiu, Weicheng; Liu, Kopin The Journal of Physical Chemistry A, Vol. 109, Issue 40 https://doi.org/10.1021/jp0536605	journal	October 2005
Imaging the Reaction Dynamics of OH + CD ₄ . 3. Isotope Effects Zhang, Bailin; Shiu, Weicheng; Liu, Kopin The Journal of Physical Chemistry A, Vol. 109, Issue 40 https://doi.org/10.1021/jp053661x	journal	October 2005
Six-dimensional and seven-dimensional quantum dynamics study of the OH + CH ₄ → H ₂ O + CH ₃ reaction Song, Hongwei; Lee, Soo-Ying; Yang, Minghui The Journal of Chemical Physics, Vol. 139, Issue 15 https://doi.org/10.1063/1.4825100	journal	October 2013
Effects of reactant rotation on the dynamics of the OH + CH ₄ → H ₂ O + CH ₃ reaction: A six-dimensional study Song, Hongwei; Li, Jun; Jiang, Bin The Journal of Chemical Physics, Vol. 140, Issue 8 https://doi.org/10.1063/1.4866426	journal	February 2014
QCT dynamics study of the reaction of hydroxyl radical and methane using a new ab initio fitted full-dimensional analytical potential energy surface Espinosa-Garcia, Joaquin; Corchado, Jose C. Theoretical Chemistry Accounts, Vol. 134, Issue 2 https://doi.org/10.1007/s00214-014-1607-1	journal	January 2015
Communication: An accurate full 15 dimensional permutationally invariant potential energy surface for the OH + CH ₄ → H ₂ O + CH ₃ reaction Li, Jun; Guo, Hua The Journal of Chemical Physics, Vol. 143, Issue 22 https://doi.org/10.1063/1.4937570	journal	December 2015
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 Srinivasan, N. K.; Su, M. -C.; Sutherland, J. W. The Journal of Physical Chemistry A, Vol. 109, Issue 9 https://doi.org/10.1021/jp040679j	journal	March 2005
Anomalous Λ-Doubling in the Infrared Spectrum of the Hydroxyl Radical in Helium Nanodroplets Raston, Paul L.; Liang, Tao; Douberly, Gary E. The Journal of Physical Chemistry A, Vol. 117, Issue 34 https://doi.org/10.1021/jp312335q	journal	February 2013
Observation of the Q (3/2) Λ-doublet transitions for X ² Π _3/2 OD in helium nanodroplets Raston, Paul L.; Liang, Tao; Douberly, Gary E. Molecular Physics, Vol. 112, Issue 2 https://doi.org/10.1080/00268976.2013.809807	journal	June 2013
Automation of an “Aculight” continuous-wave optical parametric oscillator Morrison, Alexander M.; Liang, Tao; Douberly, Gary E. Review of Scientific Instruments, Vol. 84, Issue 1 https://doi.org/10.1063/1.4776179	journal	January 2013
Infrared Spectroscopy of (HCl) _m (H ₂ O) _n Clusters in Helium Nanodroplets: Definitive Assignments in the HCl Stretch Region Morrison, Alexander M.; Flynn, Steven D.; Liang, Tao The Journal of Physical Chemistry A, Vol. 114, Issue 31 https://doi.org/10.1021/jp104545j	journal	August 2010
Infrared spectroscopy of HOOO and DOOO in ⁴ He nanodroplets Raston, Paul L.; Liang, Tao; Douberly, Gary E. The Journal of Chemical Physics, Vol. 137, Issue 18 https://doi.org/10.1063/1.4764298	journal	November 2012
Helium nanodroplet isolation rovibrational spectroscopy: Methods and recent results Callegari, Carlo; Lehmann, Kevin K.; Schmied, Roman The Journal of Chemical Physics, Vol. 115, Issue 22 https://doi.org/10.1063/1.1418746	journal	January 2001
Infrared rovibrational spectroscopy of OH–C ₂ H ₂ in ⁴ He nanodroplets: Parity splitting due to partially quenched electronic angular momentum Douberly, Gary E.; Raston, Paul L.; Liang, Tao The Journal of Chemical Physics, Vol. 142, Issue 13 https://doi.org/10.1063/1.4916394	journal	April 2015
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) Hernandez, Federico J.; Brice, Joseph T.; Leavitt, Christopher M. The Journal of Chemical Physics, Vol. 143, Issue 16 https://doi.org/10.1063/1.4933432	journal	October 2015
Infrared Stark and Zeeman spectroscopy of OH–CO: The entrance channel complex along the OH + CO → trans-HOCO reaction pathway Brice, Joseph T.; Liang, Tao; Raston, Paul L. The Journal of Chemical Physics, Vol. 145, Issue 12 https://doi.org/10.1063/1.4963226	journal	September 2016
PGOPHER: A program for simulating rotational, vibrational and electronic spectra Western, Colin M. Journal of Quantitative Spectroscopy and Radiative Transfer, Vol. 186 https://doi.org/10.1016/j.jqsrt.2016.04.010	journal	January 2017
Solvent mediated vibrational relaxation: Superfluid helium droplet spectroscopy of HCN dimer Nauta, K.; Miller, R. E. The Journal of Chemical Physics, Vol. 111, Issue 8 https://doi.org/10.1063/1.479627	journal	August 1999
The hydrogen fluoride dimer in liquid helium: A prototype system for studying solvent effects on hydrogen bonding Nauta, K.; Miller, R. E. The Journal of Chemical Physics, Vol. 113, Issue 22 https://doi.org/10.1063/1.1289824	journal	December 2000
Infrared Action Spectroscopy and Dissociation Dynamics of the HOOO Radical Derro, Erika L.; Murray, Craig; Sechler, Timothy D. The Journal of Physical Chemistry A, Vol. 111, Issue 45 https://doi.org/10.1021/jp0760915	journal	November 2007

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