Issue 8, 2012
From the journal:

Physical Chemistry Chemical Physics

Raman spectrum of supercritical C18O2 and re-evaluation of the Fermi resonance

Charles F. Windisch, Jr.,*a   Vassiliki-Alexandra Glezakou,*b   Paul F. Martin,c   B. Peter McGraild  and  Herbert T. Schaefe  

* Corresponding authors

a Material Sciences FCSD, Pacific Northwest National Laboratory, PO Box 999, Richland, WA, USA
E-mail: cf.windisch@pnl.gov

b Chemical Physics and Analysis FCSD, Pacific Northwest National Laboratory, PO Box 999, Richland, WA, USA
E-mail: Vanda.Glezakou@pnnl.gov

c Geosciences EED, Pacific Northwest National Laboratory, PO Box 999, Richland, WA, USA

d Energy Processes and Materials EED, Pacific Northwest National Laboratory, PO Box 999, Richland, WA, USA

e Geochemistry FCSD, Pacific Northwest National Laboratory, PO Box 999, Richland, WA, USA

Abstract

We report the first Raman spectra of fully 18O-labeled supercritical CO2 (scCO2) and various isotopic mixtures. The experimental results, coupled with ab initio molecular dynamics calculations, demonstrate that the frequencies assigned to the Fermi dyad of the CO2 molecule transpose upon isotopic labeling of both oxygen atoms. Although the transposition of the Fermi dyad of CO2 gas due to isotopic substitution has been discussed before, this is the first confirmation of the effect in the Raman spectrum of the supercritical fluid and provides necessary groundwork for future Raman spectroscopy studies of reactions in this important medium. More importantly, the work yields a quantitative assessment of the mixing of states upon labeling that provides the needed clarification concerning the pedigree of the assignments for the dyad of CO2 under supercritical conditions.

Graphical abstract: Raman spectrum of supercritical C18O2 and re-evaluation of the Fermi resonance

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Article information

DOI
https://doi.org/10.1039/C1CP22349F
Article type
Paper
Submitted
19 Jul 2011
Accepted
28 Oct 2011
First published
14 Nov 2011

Phys. Chem. Chem. Phys., 2012,14, 2560-2566

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Raman spectrum of supercritical C18O2 and re-evaluation of the Fermi resonance

C. F. Windisch, V. Glezakou, P. F. Martin, B. P. McGrail and H. T. Schaef, Phys. Chem. Chem. Phys., 2012, 14, 2560 DOI: 10.1039/C1CP22349F

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