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Vacuum ultraviolet photoionization cross section of the hydroxyl radical

Dodson, Leah G. and Savee, John D. and Gozem, Samer and Shen, Linhan and Krylov, Anna I. and Taatjes, Craig A. and Osborn, David L. and Okumura, Mitchio (2018) Vacuum ultraviolet photoionization cross section of the hydroxyl radical. Journal of Chemical Physics, 148 (18). Art. No. 184302. ISSN 0021-9606.

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The absolute photoionization spectrum of the hydroxyl (OH) radical from 12.513 to 14.213 eV was measured by multiplexed photoionization mass spectrometry with time-resolved radical kinetics. Tunable vacuum ultraviolet (VUV) synchrotron radiation was generated at the Advanced Light Source. OH radicals were generated from the reaction of O(^1D) + H_2O in a flow reactor in He at 8 Torr. The initial O(^1D) concentration, where the atom was formed by pulsed laser photolysis of ozone, was determined from the measured depletion of a known concentration of ozone. Concentrations of OH and O(^3P) were obtained by fitting observed time traces with a kinetics model constructed with literature rate coefficients. The absolute cross section of OH was determined to be σ(13.436 eV) = 3.2 ± 1.0 Mb and σ(14.193 eV) = 4.7 ± 1.6 Mb relative to the known cross section for O(^3P) at 14.193 eV. The absolute photoionization spectrum was obtained by recording a spectrum at a resolution of 8 meV (50 meV steps) and scaling to the single-energy cross sections. We computed the absolute VUV photoionization spectrum of OH and O(^3P) using equation-of-motion coupled-cluster Dyson orbitals and a Coulomb photoelectron wave function and found good agreement with the observed absolute photoionization spectra.

Item Type:Article
Related URLs:
URLURL TypeDescription
Dodson, Leah G.0000-0001-5960-056X
Gozem, Samer0000-0002-6429-2853
Shen, Linhan0000-0003-3871-655X
Krylov, Anna I.0000-0001-6788-5016
Taatjes, Craig A.0000-0002-9271-0282
Osborn, David L.0000-0003-4304-8218
Okumura, Mitchio0000-0001-6874-1137
Additional Information:© 2018 Published by AIP Publishing. Received 30 January 2018; accepted 17 April 2018; published online 8 May 2018. This research was supported by the National Science Foundation Grant No. CHE-1413712 and the National Aeronautics and Space Administration’s (NASA) Upper Atmospheric Research Program Grant No. NNX12AE01G. A.I.K. acknowledges support by the United States Department of Energy, Basic Energy Sciences through the No. DE-FG02-05ER15685 grant. L.G.D. was supported by an EPA STAR Fellowship and a Sandia Campus Executive Laboratory Directed Research and Development (LDRD) project. L.S. was supported by NASA Headquarters under the NASA Earth and Space Science Fellowship Program—Grant No. NNX14AO60H. The participation of D.L.O., J.D.S., and C.A.T. and the development and maintenance of the MPIMS apparatus are based upon work supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Sandia National Laboratories is a multi-mission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC., a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under Contract No. DE-NA0003525. The views expressed in the article do not necessarily represent the views of the U.S. Department of Energy or the United States Government. The research conducted used resources of the Advanced Light Source, which is a DOE Office of the Science User Facility at Lawrence Berkeley National Laboratory under Contract No. DE-AC02-05CH11231.
Funding AgencyGrant Number
Department of Energy (DOE)DE-FG02-05ER15685
Environmental Protection Agency (EPA)UNSPECIFIED
Sandia National LaboratoriesUNSPECIFIED
NASA Earth and Space Science FellowshipNNX14AO60H
Department of Energy (DOE)DE-NA0003525
Department of Energy (DOE)DE-AC02-05CH11231
Issue or Number:18
Record Number:CaltechAUTHORS:20180508-111346839
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Official Citation:Vacuum ultraviolet photoionization cross section of the hydroxyl radical. Leah G. Dodson, John D. Savee, Samer Gozem, Linhan Shen, Anna I. Krylov, Craig A. Taatjes, David L. Osborn, and Mitchio Okumura. The Journal of Chemical Physics 2018 148:18
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86281
Deposited By: Tony Diaz
Deposited On:08 May 2018 20:04
Last Modified:03 Oct 2019 19:41

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