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Vibration-rotation pattern in acetylene. II. Introduction of Coriolis coupling in the global model and analysis of emission spectra of hot acetylene around
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10.1063/1.3200928
/content/aip/journal/jcp/131/11/10.1063/1.3200928
http://aip.metastore.ingenta.com/content/aip/journal/jcp/131/11/10.1063/1.3200928

Figures

Image of FIG. 1.
FIG. 1.

High resolution FTIR emission spectra of acetylene in the spectral range recorded at 1355 K. The intensities were corrected for the instrumental transmission function (see text).

Image of FIG. 2.
FIG. 2.

Portion of the FTIR emission spectrum of heated at 1355 K. Lines in the and bands are assigned.

Image of FIG. 3.
FIG. 3.

Set of hot bands accessing lower substates with 3 and 4 quanta of bending excitation, together with hot bands involving , analyzed in from the analysis of hot emission spectra around . The vibrational substates are assigned using in terms of the dominant zero order contribution in the eigenvector for the lowest existing -value, with their symmetry species indicated. The scale is arbitrarily expanded for some levels, for clarity.

Image of FIG. 4.
FIG. 4.

Portion of the FTIR emission spectrum of recorded at 1355 K. Only lines involving cold bands and the series of hot bands with and are assigned on the observed spectrum (upper) and are simulated on the calculated spectrum (lower part). They are all lines. The labels are as follows: ; ; ; ; . They correspond to the dominant zero order contribution in the eigenvector for the lowest existing -value The and symmetries are indicated whenever relevant.

Image of FIG. 5.
FIG. 5.

Portion of the FTIR emission spectrum of recorded at 1355 K, observed (exp) and simulated [(a)–(d)]. Lines involving cold bands (a) and then the first (b), second (c), and third (d) series of assigned hot bands are successively included in the simulation.

Image of FIG. 6.
FIG. 6.

Reduced energy graph (in ) defined as as a function of . The relevant substates are labeled using , , in terms of the dominant zero order contribution in the eigenvector for the lowest existing -value. Full (empty) dots indicate observed levels successfully (unsuccessfully) accounted for in the fitting procedure. Full and dashed lines indicate - and - parity substates, respectively. The color code is adapted to the substate symmetry. Part (a) highlights vibration-rotation states in interacting through 3/245 anharmonic resonance and rotational -type resonance terms, in particular. The avoided crossing discussed in the text is highlighted using a full circle. Dotted circles indicate other level energies significantly affected by Coriolis couplings. The relevant color code is, in red, and, in pink, . Part (b) highlights two of the 2/444 Coriolis coupling schemes affecting some of the substates in Fig. 6(a). Levels previously not well calculated are now precisely reproduced, as identified using brown triangles, when introducing this interaction scheme in the global model. In addition, new lines could be assigned on the spectrum, leading to report new levels on the graph, identified using red squares.

Image of FIG. 7.
FIG. 7.

Scheme of the polyad in from the various components. Rotational -type resonance and Coriolis interactions, with and , respectively, are highlighted using dashed and plain lines, respectively.

Image of FIG. 8.
FIG. 8.

Reduced energy graph (in ) defined as in function of , presenting vibration-rotation substates in interacting through the 2/444 Coriolis coupling. The relevant substates are labeled using , , in terms of the dominant zero order contribution in the eigenvector for the lowest existing -value. Full dots indicate levels reported by Moss et al. (Ref. 29), successfully accounted for in the fitting procedure. Full and dashed lines indicate - and - parity states, respectively. The color code is adapted to the substate symmetry: in red, ; in blue, ; in pink, ; in light blue, .

Tables

Generic image for table
Table I.

Vibrational substates newly reported in identified using , , in terms of the dominant zero order contribution in the eigenvector for the lowest existing -value. The state origin as defined in Eq. (3) and associated rotational parameters determined as explained in the text are provided. The value of is listed as well as the maximum -value of the vibration-rotation levels selected for the individual substate fitting procedure.

Generic image for table
Table II.

Interaction matrix highlighting the dominant contributions in the perturbation between (in bold) the (using , ) and substates in , illustrated in Fig. 6(a). Only half of the symmetric matrix is presented.

Generic image for table
Table III.

Synthetic information on the vibrational bands and vibration-rotation lines assigned in the analysis of the hot emission spectra and kept in the acetylene database for the global fit procedure. It includes the upper and lower substate identifications using , , in terms of the dominant zero order contribution in the eigenvector for the lowest existing -values, the number of fitted (fit) and assigned (ass) lines, the minimum and maximum -values of the lines introduced in the acetylene database for the global fit, and the experimental accuracy ( in ) on the unblended lines wavenumbers.

Generic image for table
Table IV.

Vibration-rotation parameters (in ) with their uncertainties for the global fit of .

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/content/aip/journal/jcp/131/11/10.1063/1.3200928
2009-09-15
2014-04-21
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Vibration-rotation pattern in acetylene. II. Introduction of Coriolis coupling in the global model and analysis of emission spectra of hot acetylene around 3 μm
http://aip.metastore.ingenta.com/content/aip/journal/jcp/131/11/10.1063/1.3200928
10.1063/1.3200928
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