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Photodissociation dynamics of the phenyl radical via photofragment translational spectroscopy
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10.1063/1.3473743
/content/aip/journal/jcp/133/7/10.1063/1.3473743
http://aip.metastore.ingenta.com/content/aip/journal/jcp/133/7/10.1063/1.3473743
View: Figures

Figures

Image of FIG. 1.
FIG. 1.

Potential energy surface for the phenyl radical as calculated by Madden et al. (Ref. 26) at the G2M level of theory. The asymptotic channels 1, 2, and 3 are indicated.

Image of FIG. 2.
FIG. 2.

Schematic of apparatus showing the radical source, photodissociation laser, and rotating mass spectrometer detector.

Image of FIG. 3.
FIG. 3.

Mass spectra of the molecular beam of nitrosobenzene in helium taken with the pyrolytic source unheated in the upper trace and heated in the lower trace.

Image of FIG. 4.
FIG. 4.

Characteristic TOF spectra for fragments collected at , 5°, 6°, and 8° obtained from 248 and 193 nm photodissociation of . The fits to these TOF spectra (solid lines) are generated from the distributions in Figs. 8 and 9, respectively.

Image of FIG. 5.
FIG. 5.

Characteristic TOF spectra for and fragments collected at , 12°, and 15° obtained from 193 nm photodissociation of . A single distribution, shown in Fig. 10, was used to fit these spectra.

Image of FIG. 6.
FIG. 6.

TOF spectra of at 193 nm showing contributions from daughter ions of mass 76 and mass 51 fragments. In each spectrum, these contributions are fit, respectively, with a dotted line using the distribution in Fig. 9 and a dashed line using the distribution in Fig. 10. The solid black line shows the sum of the dashed and dotted simulations.

Image of FIG. 7.
FIG. 7.

Newton diagram for the phenyl radical photodissociation at 193 nm. Each circle represents the maximum center-of-mass speeds of product photofragments. The solid black circles represent the fragments, while the dotted circle represents the fragment. Maximum laboratory scattering angles for the fragments are shown.

Image of FIG. 8.
FIG. 8.

Center-of-mass distribution from phenyl photodissociation at 248 nm to . The maximum available translational energy assumed for channel 1 is set at 37 kcal/mol. Due to the minimum laboratory detection angle of 3° for the current experimental setup, points below 5 kcal/mol are less reliable than those at higher energy.

Image of FIG. 9.
FIG. 9.

Center-of-mass distribution from phenyl photodissociation at 193 nm to form . The maximum available translational energy assumed for channel 1 is set at 72 kcal/mol. Due to the minimum laboratory detection angle of 3° for the current experimental setup, points below 5 kcal/mol are less reliable than those at higher energy.

Image of FIG. 10.
FIG. 10.

Center-of-mass distribution for the channel shown in Fig. 6. This distribution was used to fit the TOF spectra for both and 26. The maximum allowed translational energy is set at 50 kcal/mol.

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/content/aip/journal/jcp/133/7/10.1063/1.3473743
2010-08-16
2014-04-25
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Photodissociation dynamics of the phenyl radical via photofragment translational spectroscopy
http://aip.metastore.ingenta.com/content/aip/journal/jcp/133/7/10.1063/1.3473743
10.1063/1.3473743
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