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Title: Carbon and oxygen isotopic fractionation in the products of low-temperature VUV photodissociation of carbon monoxide

Abstract

The carbon and oxygen isotope fractionations occurring during photodissociation of carbon monoxide (CO) by vacuum ultraviolet photons (91–107 nm) at 80 K were measured and the isotopic fractionations due to direct and indirect predissociation processes individually quantified. The isotopic fractionations depend on the photodissociation wavelength. Slope values (δ' 17O/δ' 18O) in oxygen three-isotope space range from 0.75 to 1.1. The isotopic composition of the products depends on the dissociation dynamics at the upper electronic state (perturbation and coupling associated with that state), which in turn modulates the isotope effect (in this case an enrichment of minor isotopes) inside the gas column due to the saturation of major isotopologue (isotope self-shielding). An explanation in terms of isotope self-shielding would require a quantum yield of one for photodissociation of all isotopologues which is not consistent with the data.

Authors:
; ; ORCiD logo;
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1439404
Alternate Identifier(s):
OSTI ID: 1542332
Grant/Contract Number:  
[AC02-05CH11231]
Resource Type:
Published Article
Journal Name:
Chemical Physics
Additional Journal Information:
[Journal Name: Chemical Physics Journal Volume: 514 Journal Issue: C]; Journal ID: ISSN 0301-0104
Publisher:
Elsevier
Country of Publication:
Netherlands
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Isotopic Fractionation; Early Solar Nebula; Photochemistry; Oxygen and Carbon Isotopes; Predissociation

Citation Formats

Chakraborty, Subrata, Rude, Bruce, Ahmed, Musahid, and Thiemens, Mark H. Carbon and oxygen isotopic fractionation in the products of low-temperature VUV photodissociation of carbon monoxide. Netherlands: N. p., 2018. Web. doi:10.1016/j.chemphys.2018.05.022.
Chakraborty, Subrata, Rude, Bruce, Ahmed, Musahid, & Thiemens, Mark H. Carbon and oxygen isotopic fractionation in the products of low-temperature VUV photodissociation of carbon monoxide. Netherlands. doi:10.1016/j.chemphys.2018.05.022.
Chakraborty, Subrata, Rude, Bruce, Ahmed, Musahid, and Thiemens, Mark H. Mon . "Carbon and oxygen isotopic fractionation in the products of low-temperature VUV photodissociation of carbon monoxide". Netherlands. doi:10.1016/j.chemphys.2018.05.022.
@article{osti_1439404,
title = {Carbon and oxygen isotopic fractionation in the products of low-temperature VUV photodissociation of carbon monoxide},
author = {Chakraborty, Subrata and Rude, Bruce and Ahmed, Musahid and Thiemens, Mark H.},
abstractNote = {The carbon and oxygen isotope fractionations occurring during photodissociation of carbon monoxide (CO) by vacuum ultraviolet photons (91–107 nm) at 80 K were measured and the isotopic fractionations due to direct and indirect predissociation processes individually quantified. The isotopic fractionations depend on the photodissociation wavelength. Slope values (δ'17O/δ'18O) in oxygen three-isotope space range from 0.75 to 1.1. The isotopic composition of the products depends on the dissociation dynamics at the upper electronic state (perturbation and coupling associated with that state), which in turn modulates the isotope effect (in this case an enrichment of minor isotopes) inside the gas column due to the saturation of major isotopologue (isotope self-shielding). An explanation in terms of isotope self-shielding would require a quantum yield of one for photodissociation of all isotopologues which is not consistent with the data.},
doi = {10.1016/j.chemphys.2018.05.022},
journal = {Chemical Physics},
number = [C],
volume = [514],
place = {Netherlands},
year = {2018},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1016/j.chemphys.2018.05.022

Citation Metrics:
Cited by: 3 works
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Works referenced in this record:

Data from: Carbon and oxygen isotopic fractionation in the products of low-temperature VUV photodissociation of carbon monoxide
dataset, January 2018

  • Chakraborty, Subrata; Rude, Bruce; Ahmed, Musahid
  • UC San Diego Library Digital Collections
  • DOI: 10.6075/j0v9868d