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Elimination mechanisms of Br2 + and Br+ in photodissociation of 1,1- and 1,2-dibromoethylenes using velocity imaging technique
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10.1063/1.3584178
/content/aip/journal/jcp/134/19/10.1063/1.3584178
http://aip.metastore.ingenta.com/content/aip/journal/jcp/134/19/10.1063/1.3584178

Figures

Image of FIG. 1.
FIG. 1.

TOF mass spectra of (a) 1,2-C2H2Br2 and (b) 1,1-C2H2Br2 in the photolysis at 233 nm with the energy of 19 and 24 μJ/pulse, respectively. (c) The power dependence measurements of the Br+ and Br2 + signals dissociated from 1,2-C2H2Br2 at 233 nm.

Image of FIG. 2.
FIG. 2.

The raw images of Br2 + and Br+ acquired from photodissociation of 1,2-C2H2Br2 and 1,1-C2H2Br2 at 233 nm. The color coding is also included.

Image of FIG. 3.
FIG. 3.

Center-of-mass translational energy distributions of the Br2 + elimination channel from either 1,2-C2H2Br2 or 1,1-C2H2Br2 at 233 nm. The open circles are the experimental data and the solid lines are the fitted results.

Image of FIG. 4.
FIG. 4.

Kinetic energy distributions of Br+ fragment upon dissociation of either 1,2-C2H2Br2 or 1,1-C2H2Br2 at 233 nm. The open circles are the experimental data that are deconvoluted into one Boltzmann and two Gaussian functions for 1,2-C2H2Br2, while one Boltzmann and one Gaussian functions for 1,1-C2H2Br2. The solid lines are the sum of fitted results.

Image of FIG. 5.
FIG. 5.

Schematic diagram for probable photodissociation and photoionization pathways of dibromoethylenes (DBE) at 233 nm.

Image of FIG. 6.
FIG. 6.

Ab initio calculations of dissociation pathways for the scheme, 1,2-C2H2Br2 → C2H2 + Br2 +. 1,2-C2H2Br2 contains both cis- and trans-isomers. The calculation level is B3LYP with the basis set 6-311**G(2df, 2pd).

Image of FIG. 7.
FIG. 7.

Kinetic energy distributions of Br+ fragment dissociated from 1,2-C2H2Br2, when the laser is tuned to either a REMPI wavelength at 232.93 nm (dotted-line) or a non-REMPI wavelength at 233 nm (solid line). Their intensities are normalized.

Tables

Generic image for table
Table I.

Anisotropy parameters derived from the fragment images.

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/content/aip/journal/jcp/134/19/10.1063/1.3584178
2011-05-20
2014-04-20
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Elimination mechanisms of Br2+ and Br+ in photodissociation of 1,1- and 1,2-dibromoethylenes using velocity imaging technique
http://aip.metastore.ingenta.com/content/aip/journal/jcp/134/19/10.1063/1.3584178
10.1063/1.3584178
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