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The influence of translational and vibrational energy on the reaction of Cl with CH3D
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10.1063/1.4808378
/content/aip/journal/jcp/138/22/10.1063/1.4808378
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/22/10.1063/1.4808378

Figures

Image of FIG. 1.
FIG. 1.

Energetics of the reaction of CHD with Cl to produce either CH + DCl (left hand barrier) or CHD + HCl (right hand barrier). The barrier heights are consistent with calculations on other isotopologues and the observed relative yields of CH and CHD for different collision energies. The translation energy distributions shown in the figure correspond to the production of Cl atoms by photolysis of Cl at three different wavelengths: 309 nm, 355 nm, and 416 nm. The label 2ν marks the energy of the overtone vibration with one quantum in each of two C–H bonds.

Image of FIG. 2.
FIG. 2.

Relative yields of CH (red trace) and CHD (blue trace) from the reaction of CHD with translationally energized Cl atoms. The three sets of data are for collision energies of = 1970 cm ( = 309 nm), = 1280 cm ( = 355 nm), and = 610 cm ( = 416 nm). The relative yield of CH decreases with decreasing translational energy, as shown by the ratio of the areas of the features. The wavelengths on the abscissa are values in vacuum.

Image of FIG. 3.
FIG. 3.

Vibrational action spectra for the reaction of vibrationally excited CHD with Cl to produce CHD(ν) at three different relative translational energies. The comb above the spectra and the dots above individual features mark rotational transitions of the -symmetry stretching vibration. The unmarked features are transitions to the -symmetry states, and all of the spectra are normalized to the isolated transition, R(3), at 6066 cm.

Image of FIG. 4.
FIG. 4.

Product state REMPI signals for the CHD products of the reaction of vibrationally excited CHD with Cl to produce CHD(ν), having only C–H stretching excitation, and CHD(ν + ν), having both C–H stretching and bending excitation, at three different relative translational energies. The smooth black lines are fits of Lorentzian lineshapes to the features.

Tables

Generic image for table
Table I.

Photolysis wavelengths, cross sections, collisions energies, and distribution widths.

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/content/aip/journal/jcp/138/22/10.1063/1.4808378
2013-06-11
2014-04-17
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: The influence of translational and vibrational energy on the reaction of Cl with CH3D
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/22/10.1063/1.4808378
10.1063/1.4808378
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