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

Chakraborty, Subrata; Rude, Bruce; Ahmed, Musahid; Thiemens, Mark H.

doi:10.1016/j.chemphys.2018.05.022

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:

Chakraborty, Subrata; Rude, Bruce;

; Thiemens, Mark H.

Publication Date:: 2018-10-01

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

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

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.

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                    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.  https://doi.org/10.1016/j.chemphys.2018.05.022

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                    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.  https://doi.org/10.1016/j.chemphys.2018.05.022.

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@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}

}

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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

Works referencing / citing this record:

Use of Isotope Effects To Understand the Present and Past of the Atmosphere and Climate and Track the Origin of Life
journal, February 2019

Thiemens, Mark H.; Lin, Mang
Angewandte Chemie, Vol. 131, Issue 21
DOI: 10.1002/ange.201812322

Use of Isotope Effects To Understand the Present and Past of the Atmosphere and Climate and Track the Origin of Life
journal, May 2019

Thiemens, Mark H.; Lin, Mang
Angewandte Chemie International Edition, Vol. 58, Issue 21
DOI: 10.1002/anie.201812322

The discovery of chemically produced mass independent isotope effects: The physical chemistry basis and applications to the early solar system, planetary atmospheres, and the origin of life: Acceptance Speech of the Leonard Medal July 2017
journal, October 2018

Thiemens, Mark H.
Meteoritics & Planetary Science, Vol. 54, Issue 1
DOI: 10.1111/maps.13198

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Abstract

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