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Title: Internal energy dependence of the photodissociation dynamics of O 3 - using cryogenic photoelectron-photofragment coincidence spectroscopy

Abstract

Photoelectron-photofragment coincidence (PPC) spectra of ozonide, O 3 -, were measured at 388 nm (E = 3.20 eV) using a newly constructed cryogenic octopole accumulation trap coupled to a PPC spectrometer. The photoelectron spectra reveal three processes consisting of a stable photodetachment channel, and two distinct photodissociation pathways yielding (1) O 2 + O - or (2) O + O 2 -. The first photodissociation pathway is observed in the PPC spectra by photodetachment of the O - product by a second photon, and produces electronically excited O 2( 1Δ g). The O 2 - product of the second photodissociation pathway undergoes autodetachment for O 2 -( 2Π g, v" > 4), a process greatly enhanced by vibrational excitation of the precursor O 3 -. Cooling anions thermalized at 300 K to <17 K in a cryogenic octopole accumulation trap essentially turns off this autodetachment pathway. The product kinetic energy distribution in coincidence with the autodetached electrons from O 2 -(v′′ = 4) exhibits resolved features consistent with bend (ν 2), asymmetric stretch (ν 3) and a stretching combination band (ν 1 + ν 3) in the intermediate electronic state, illustrating the insights that can be gained from kinematicallymore » complete measurements. Finally, these results are discussed in the context of the low-lying excited states of O 3 -.« less

Authors:
 [1];  [1];  [1]; ORCiD logo [1]
  1. Univ. of California, San Diego, CA (United States). Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
Univ. of California, San Diego, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1535315
Alternate Identifier(s):
OSTI ID: 1378813
Grant/Contract Number:  
[FG03-98ER14879]
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
[ Journal Volume: 147; Journal Issue: 9]; 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; chemistry; physics

Citation Formats

Shen, Ben B., Benitez, Yanice, Lunny, Katharine G., and Continetti, Robert E. Internal energy dependence of the photodissociation dynamics of O3- using cryogenic photoelectron-photofragment coincidence spectroscopy. United States: N. p., 2017. Web. doi:10.1063/1.4986500.
Shen, Ben B., Benitez, Yanice, Lunny, Katharine G., & Continetti, Robert E. Internal energy dependence of the photodissociation dynamics of O3- using cryogenic photoelectron-photofragment coincidence spectroscopy. United States. doi:10.1063/1.4986500.
Shen, Ben B., Benitez, Yanice, Lunny, Katharine G., and Continetti, Robert E. Wed . "Internal energy dependence of the photodissociation dynamics of O3- using cryogenic photoelectron-photofragment coincidence spectroscopy". United States. doi:10.1063/1.4986500. https://www.osti.gov/servlets/purl/1535315.
@article{osti_1535315,
title = {Internal energy dependence of the photodissociation dynamics of O3- using cryogenic photoelectron-photofragment coincidence spectroscopy},
author = {Shen, Ben B. and Benitez, Yanice and Lunny, Katharine G. and Continetti, Robert E.},
abstractNote = {Photoelectron-photofragment coincidence (PPC) spectra of ozonide, O3-, were measured at 388 nm (Ehν = 3.20 eV) using a newly constructed cryogenic octopole accumulation trap coupled to a PPC spectrometer. The photoelectron spectra reveal three processes consisting of a stable photodetachment channel, and two distinct photodissociation pathways yielding (1) O2 + O- or (2) O + O2-. The first photodissociation pathway is observed in the PPC spectra by photodetachment of the O- product by a second photon, and produces electronically excited O2(1Δg). The O2- product of the second photodissociation pathway undergoes autodetachment for O2-(2Πg, v" > 4), a process greatly enhanced by vibrational excitation of the precursor O3-. Cooling anions thermalized at 300 K to <17 K in a cryogenic octopole accumulation trap essentially turns off this autodetachment pathway. The product kinetic energy distribution in coincidence with the autodetached electrons from O2-(v′′ = 4) exhibits resolved features consistent with bend (ν2), asymmetric stretch (ν3) and a stretching combination band (ν1 + ν3) in the intermediate electronic state, illustrating the insights that can be gained from kinematically complete measurements. Finally, these results are discussed in the context of the low-lying excited states of O3-.},
doi = {10.1063/1.4986500},
journal = {Journal of Chemical Physics},
number = [9],
volume = [147],
place = {United States},
year = {2017},
month = {9}
}

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