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Transient dimer formation in supercritical carbon dioxide as seen from Raman scattering
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10.1063/1.2833493
/content/aip/journal/jcp/128/7/10.1063/1.2833493
http://aip.metastore.ingenta.com/content/aip/journal/jcp/128/7/10.1063/1.2833493

Figures

Image of FIG. 1.
FIG. 1.

Polarized and depolarized Raman spectra of the bending vibrational mode of at ; (-*-*-) ; (-▴-▴-) . The spectra of the empty cell (—) are also reported for comparison.

Image of FIG. 2.
FIG. 2.

Polarized and depolarized Raman spectra of the bending vibrational mode of at after corrections (see text). Fitted Lorentzian profiles (- - -) are also reported.

Image of FIG. 3.
FIG. 3.

Diagrammatic representation of the ab initio calculated Raman spectrum of the parallel slipped dimer in the bending region of : vibrational transitions are centered at their anharmonic frequency values with their calculated intensity. For the sake of convenience and to guide the eyes, each transition has also been represented by a Lorentzian profile (with an arbitrary full width of ) and the resulting profile is displayed as a solid line.

Image of FIG. 4.
FIG. 4.

Diagrammatic representation of the ab initio calculated Raman spectrum of the cyclic and noncyclic trimers in the bending region of : vibrational transitions are centered at their harmonic frequencies with their calculated intensity. Each transition has also been represented by a Lorentzian profile (with an arbitrary full width of ) and the resulting profiles are displayed as dash dot line for cyclic trimer and dash for noncyclic trimer. The solid line corresponds to the sum of the two contributions.

Image of FIG. 5.
FIG. 5.

Influence of the anharmonicity on the ab initio calculated Raman spectrum of (a) noncyclic and (b) cyclic trimers in the bending region of . As for previous figures, each transition has also been represented by a Lorentzian profile (with an arbitrary full width of ). The resulting profiles displayed as (—○—) for cyclic trimer and as (—+—) for noncyclic trimer are compared with the calculated profile associated with the parallel slipped dimer (solid line), as represented in Fig. 3.

Image of FIG. 6.
FIG. 6.

Evolution with the proportion of noncyclic trimers of the Raman profile in the bending region of from the calculated Raman profile associated with the parallel slipped dimer (solid line).

Image of FIG. 7.
FIG. 7.

Polarized Raman spectra of in the Fermi dyad domain at at different reduced density values .

Image of FIG. 8.
FIG. 8.

Comparison of experimental polarized Raman spectra of in the Fermi dyad domain at with fitted profiles to each dyad component: (a) one Lorentzian profile; (b) two Lorentzian profiles.

Image of FIG. 9.
FIG. 9.

Evolution with the reduced density of the intensity ratio of the fitted profiles on the upper and lower Fermi components at : (a) ; (b) (○) and (▴) (see text).

Image of FIG. 10.
FIG. 10.

Polarized Raman spectra in the domain between the Fermi dyad peaks at for different reduced density values (spectral resolution of ): from bottom to top 0.48, 1.55, and 1.87. The polarized and depolarized spectra at (spectral resolution of ) are displayed in the inset.

Tables

Generic image for table
Table I.

Band center position , width (FWHH) obtained by fitting Lorentzian profiles to the and Raman bands assigned to the vibrational mode of the transient complex; is the experimental depolarization ratio.

Generic image for table
Table II.

Vibrational analysis of the ∥ slipped dimer : harmonic and anharmonic frequencies, and IR and Raman intensities calculated at the MP2/aug-cc-pVDZ level. The calculated depolarization ratios are indicated in parentheses.

Generic image for table
Table III.

Vibrational analysis of trimers : harmonic and anharmonic frequencies, and IR and Raman intensities calculated at the MP2/aug-cc-pVDZ level. The calculated depolarization ratios are indicated in parentheses.

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/content/aip/journal/jcp/128/7/10.1063/1.2833493
2008-02-21
2014-04-23
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Transient dimer formation in supercritical carbon dioxide as seen from Raman scattering
http://aip.metastore.ingenta.com/content/aip/journal/jcp/128/7/10.1063/1.2833493
10.1063/1.2833493
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