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Title: Reaction dynamics of O({sup 1}D) + HCOOD/DCOOH investigated with time-resolved Fourier-transform infrared emission spectroscopy

Abstract

We investigated the reaction dynamics of O({sup 1}D) towards hydrogen atoms of two types in HCOOH. The reaction was initiated on irradiation of a flowing mixture of O{sub 3} and HCOOD or DCOOH at 248 nm. The relative vibration-rotational populations of OH and OD (1 ≦ v ≦ 4, J ≤ 15) states were determined from time-resolved IR emission recorded with a step-scan Fourier-transform spectrometer. In the reaction of O({sup 1}D) + HCOOD, the rotational distribution of product OH is nearly Boltzmann, whereas that of OD is bimodal. The product ratio [OH]/[OD] is 0.16 ± 0.05. In the reaction of O({sup 1}D) + DCOOH, the rotational distribution of product OH is bimodal, but the observed OD lines are too weak to provide reliable intensities. The three observed OH/OD channels agree with three major channels of production predicted with quantum-chemical calculations. In the case of O({sup 1}D) + HCOOD, two intermediates HOC(O)OD and HC(O)OOD are produced in the initial C−H and O−D insertion, respectively. The former undergoes further decomposition of the newly formed OH or the original OD, whereas the latter produces OD via direct decomposition. Decomposition of HOC(O)OD produced OH and OD with similar vibrational excitation, indicating efficient intramolecular vibrational relaxation, IVR. Decomposition ofmore » HC(O)OOD produced OD with greater rotational excitation. The predicted [OH]/[OD] ratio is 0.20 for O({sup 1}D) + HCOOD and 4.08 for O({sup 1}D) + DCOOH; the former agrees satisfactorily with experiments. We also observed the v{sub 3} emission from the product CO{sub 2}. This emission band is deconvoluted into two components corresponding to internal energies E = 317 and 96 kJ mol{sup −1} of CO{sub 2}, predicted to be produced via direct dehydration of HOC(O)OH and secondary decomposition of HC(O)O that was produced via decomposition of HC(O)OOH, respectively.« less

Authors:
; ;  [1];  [2];  [3];  [1]
  1. Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, Hsinchu 30010, Taiwan (China)
  2. School of Chemical Engineering - Hanoi University of Science and Technology, Hanoi (Viet Nam)
  3. Center for Computational Science and Faculty of Chemistry, Hanoi National University of Education, Hanoi (Viet Nam)
Publication Date:
OSTI Identifier:
22436612
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 141; Journal Issue: 15; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ATOMS; CARBON DIOXIDE; DECOMPOSITION; DEHYDRATION; EMISSION; EMISSION SPECTROSCOPY; EXCITATION; FOURIER TRANSFORM SPECTROMETERS; FOURIER TRANSFORMATION; IRRADIATION; MIXTURES; OZONE; RELAXATION

Citation Formats

Huang, Shang-Chen, Putikam, Raghunath, Lin, M. C., E-mail: chemmcl@emory.edu, E-mail: tsuchis@sepia.plala.or.jp, E-mail: yplee@mail.nctu.edu.tw, Tsuchiya, Soji, Nghia, N. T., Nguyen, Hue M. T., Lee, Yuan-Pern, and Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan. Reaction dynamics of O({sup 1}D) + HCOOD/DCOOH investigated with time-resolved Fourier-transform infrared emission spectroscopy. United States: N. p., 2014. Web. doi:10.1063/1.4897418.
Huang, Shang-Chen, Putikam, Raghunath, Lin, M. C., E-mail: chemmcl@emory.edu, E-mail: tsuchis@sepia.plala.or.jp, E-mail: yplee@mail.nctu.edu.tw, Tsuchiya, Soji, Nghia, N. T., Nguyen, Hue M. T., Lee, Yuan-Pern, & Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan. Reaction dynamics of O({sup 1}D) + HCOOD/DCOOH investigated with time-resolved Fourier-transform infrared emission spectroscopy. United States. https://doi.org/10.1063/1.4897418
Huang, Shang-Chen, Putikam, Raghunath, Lin, M. C., E-mail: chemmcl@emory.edu, E-mail: tsuchis@sepia.plala.or.jp, E-mail: yplee@mail.nctu.edu.tw, Tsuchiya, Soji, Nghia, N. T., Nguyen, Hue M. T., Lee, Yuan-Pern, and Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan. 2014. "Reaction dynamics of O({sup 1}D) + HCOOD/DCOOH investigated with time-resolved Fourier-transform infrared emission spectroscopy". United States. https://doi.org/10.1063/1.4897418.
@article{osti_22436612,
title = {Reaction dynamics of O({sup 1}D) + HCOOD/DCOOH investigated with time-resolved Fourier-transform infrared emission spectroscopy},
author = {Huang, Shang-Chen and Putikam, Raghunath and Lin, M. C., E-mail: chemmcl@emory.edu, E-mail: tsuchis@sepia.plala.or.jp, E-mail: yplee@mail.nctu.edu.tw and Tsuchiya, Soji and Nghia, N. T. and Nguyen, Hue M. T. and Lee, Yuan-Pern and Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan},
abstractNote = {We investigated the reaction dynamics of O({sup 1}D) towards hydrogen atoms of two types in HCOOH. The reaction was initiated on irradiation of a flowing mixture of O{sub 3} and HCOOD or DCOOH at 248 nm. The relative vibration-rotational populations of OH and OD (1 ≦ v ≦ 4, J ≤ 15) states were determined from time-resolved IR emission recorded with a step-scan Fourier-transform spectrometer. In the reaction of O({sup 1}D) + HCOOD, the rotational distribution of product OH is nearly Boltzmann, whereas that of OD is bimodal. The product ratio [OH]/[OD] is 0.16 ± 0.05. In the reaction of O({sup 1}D) + DCOOH, the rotational distribution of product OH is bimodal, but the observed OD lines are too weak to provide reliable intensities. The three observed OH/OD channels agree with three major channels of production predicted with quantum-chemical calculations. In the case of O({sup 1}D) + HCOOD, two intermediates HOC(O)OD and HC(O)OOD are produced in the initial C−H and O−D insertion, respectively. The former undergoes further decomposition of the newly formed OH or the original OD, whereas the latter produces OD via direct decomposition. Decomposition of HOC(O)OD produced OH and OD with similar vibrational excitation, indicating efficient intramolecular vibrational relaxation, IVR. Decomposition of HC(O)OOD produced OD with greater rotational excitation. The predicted [OH]/[OD] ratio is 0.20 for O({sup 1}D) + HCOOD and 4.08 for O({sup 1}D) + DCOOH; the former agrees satisfactorily with experiments. We also observed the v{sub 3} emission from the product CO{sub 2}. This emission band is deconvoluted into two components corresponding to internal energies E = 317 and 96 kJ mol{sup −1} of CO{sub 2}, predicted to be produced via direct dehydration of HOC(O)OH and secondary decomposition of HC(O)O that was produced via decomposition of HC(O)OOH, respectively.},
doi = {10.1063/1.4897418},
url = {https://www.osti.gov/biblio/22436612}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 15,
volume = 141,
place = {United States},
year = {Tue Oct 21 00:00:00 EDT 2014},
month = {Tue Oct 21 00:00:00 EDT 2014}
}