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The vibrationally mediated photodissociation of Cl2
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10.1063/1.4754160
/content/aip/journal/jcp/137/12/10.1063/1.4754160
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/12/10.1063/1.4754160

Figures

Image of FIG. 1.
FIG. 1.

The relevant diabatic (left) and adiabatic (right) potentials11 for the electronically excited states of Cl2 included in the dynamics calculation.

Image of FIG. 2.
FIG. 2.

Cl(2P3/2) ion images (left panels), and corresponding Fourier moments (—–) and fits (- - -) (right panels) for linearly polarized pump and probe radiation obtained using the 2P1/22P3/2 transition following photodissociation at 398 nm. The Fourier moments are colour coded, C 0 (black), C 2 (green), C 4 (yellow), C 6 (grey).32,33

Image of FIG. 3.
FIG. 3.

Calculated partial photodissociation cross sections showing the contributions from all of the states included in the Cl2(v = 1) dynamical calculations (—–). The data are compared with similar results for Cl2(v = 0) (− − −).10 (a) Partial photodissociation cross sections for states correlating with the ground state product channel (Cl + Cl). (b) Closeup of partial photodissociation cross sections for states correlating with the excited state product channel (Cl + Cl*). The data for Cl2(v = 1) (—–) are compared with those for Cl2(v = 0) (− − −).10

Image of FIG. 4.
FIG. 4.

The ratio of partial photodissociation yields (in black) from the Cl2(v = 0) and Cl2(v = 1) calculations, i.e., σ v = 1 v = 0 weighted by the initial state vibrational populations at the given temperature. The calculated data are compared with the experimental (v = 1)/(v = 0) ratio (in red, with points) determined from the intensities of the v = 1 and v = 0 signals in the ion images. The experimental errors (not shown) are typically around 10% for the Cl + Cl channel, and somewhat larger for the Cl + Cl* channel. The calculations are based on vibrational temperatures of 150, 200, and 298 K. The data shown in (a) and (b) correspond to the ground (Cl + Cl) and excited (Cl + Cl*) state product channels, respectively.

Image of FIG. 5.
FIG. 5.

(a) The branching fraction, Cl*/Cl, as defined in the text, for Cl2(v = 1) (—–) and Cl2(v = 0) (- - -) (shown in red). The experimental v = 1 data are shown as black open circles. (b) Spatial anisotropy parameter, β, for Cl2(v = 1) (—–) and Cl2(v = 0) (- - -). In this panel, the experimental data are represented by open circles, with red points and lines corresponding to the ground state product channel (Cl + Cl) and black points and lines to the excited product channel (Cl + Cl*).

Image of FIG. 6.
FIG. 6.

Incoherent (a) and coherent (b) K = 2 alignment parameters for Cl2(v = 1) (—–) and Cl2(v = 0) (- - -) photodissociation into the excited state product channel (Cl + Cl*). The experimental v = 1 data returned from the fits to the Cl(2P3/2) Fourier moments are represented by open circles.

Image of FIG. 7.
FIG. 7.

Incoherent (a) and coherent (b) K = 2 alignment parameters for Cl2(v = 1) (—–) and Cl2(v = 0) (- - -) photodissociation into the ground state product channel (Cl + Cl). The experimental v = 1 data returned from the fits to the Cl(2P3/2) Fourier moments are represented by open circles.

Image of FIG. 8.
FIG. 8.

Incoherent K = 1 and 3 orientation parameters for Cl2(v = 1) (—–) and Cl2(v = 0) (- - -) dissociation into the ground state product channel (Cl + Cl). The experimental v = 1 data returned from the fits to Cl(2P3/2) Fourier moments are represented by open circles.

Tables

Generic image for table
Table I.

The ungerade electronic states of the Cl2 molecule correlating with two 2P J Cl fragments which are included in the dynamics calculations. Hunds case (c) labels are given in parenthesis.

Generic image for table
Table II.

Ab initio transition dipole moments (TDM)11 used in the wavepacket dynamics calculation.

Generic image for table
Table III.

Parameters used in the QM wavepacket calculations.

Generic image for table
Table IV.

Spatial anisotropy and angular momentum polarization parameters for the Cl(2P3/2) fragments as returned from the fits to experimental Fourier moments. For wavelengths 376–420 nm, the data shown are for the ground state (Cl + Cl) product channel. For 450 nm and 470 nm, the data correspond to the excited state (Cl + Cl*) product channel. Errors (1σ) in the last digit(s) are given in parentheses.

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/content/aip/journal/jcp/137/12/10.1063/1.4754160
2012-09-27
2014-04-21
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: The vibrationally mediated photodissociation of Cl2
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/12/10.1063/1.4754160
10.1063/1.4754160
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