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Electronic polarization effects in the photodissociation of Cl2
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10.1063/1.4704830
/content/aip/journal/jcp/136/16/10.1063/1.4704830
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/16/10.1063/1.4704830

Figures

Image of FIG. 1.
FIG. 1.

(a) Selection of Cl ion images following photodissociation of Cl2 at a range of wavelengths. The ion images were recorded in the HH pump-probe geometry, and used the 2P1/22P3/2 REMPI transition at 236.2 nm. (b) Ion images for different pump-probe geometries (left), Fourier moments (—–) and fits (- − − ) (right) to the Cl data obtained for photolysis at 355 nm, with the n = 0, 2, and 4 experimental Fourier moments shown as red, green, and yellow continuous lines. Images were recorded using the 2P1/22P3/2 REMPI transition at 236.2 nm.

Image of FIG. 2.
FIG. 2.

Ion images for RR and RL circular polarizations of pump and probe lasers, respectively (left), Fourier moments (—–) and fits (- − − ) (right) to the Cl data, with the n = 0, 2, and 4 experimental Fourier moments shown as red, green, and yellow continuous lines. Images recorded using the 2P1/22P3/2 REMPI transition at 236.2 nm.

Image of FIG. 3.
FIG. 3.

Speed distributions, P(v), returned from the fits to the Cl Fourier moments at the wavelengths indicated.

Image of FIG. 4.
FIG. 4.

Examples of REMPI TOF data taken at 320 nm and 330 nm. Panels (a) and (b) show symmetrized profiles and simulated fits for the 35Cl* and 37Cl* fragments, respectively, for photolysis at 320 nm at the double magic angle geometry; the profiles clearly show the effects of core extraction. Panels (c) and (d) show the effects of vector correlations in determining the shape of the TOF data. Specifically, panel (c) shows the difference profiles and best fit for photolysis at 320 nm using geometry pair I, Δg I(x), while panel (d) shows the difference profile and best fits to the difference profile obtained in geometry pair IV, Δg IV(x), for photolysis at 330 nm and detection of 35Cl*.

Image of FIG. 5.
FIG. 5.

Cl*(2P1/2)/Cl(2P3/2) branching ratio determined from the experimental imaging data (circles) and compared to the theoretical study presented in the accompanying paper (—–),22 and with the previous measurements by Samartzis et al. (filled squares).13 Note that the sharp drop in the branching ratio at 475 nm corresponds to the threshold for making Cl*.

Image of FIG. 6.
FIG. 6.

Spatial anisotropy parameter, β, returned from the fits to the Cl(2P3/2) Fourier moments of the ion images (circles) and to the TOF REMPI data (open squares), and compared to the calculated data presented in the accompanying paper (—–).22 The data marked with crossed circles are for the excited state channel, but as observed on the Cl*(2P1/2) fragment. Data are shown for dissociation into both the ground (red) and excited (black) state product channels. Previously reported values by Samartzis et al. 13 are represented by solid squares.

Image of FIG. 7.
FIG. 7.

Incoherent K = 2 alignment parameters returned from the fits to the Cl Fourier moments of the ion images (open circles) and the TOF REMPI data (solid triangles), and compared to theory (—–).22 Data shown for dissociation into the ground state product channel. Previous measurements by Brouard and coworkers at 308 nm (solid circles),12 Zare and coworkers at 320 nm (open squares),10 and Bracker et al. at 355 nm (open triangles)9 are also shown.

Image of FIG. 8.
FIG. 8.

Coherent K = 2 alignment parameters returned from the fits to the Cl Fourier moments of the ion images (open circles) and the TOF REMPI data (solid triangles), and compared to the theoretical values (—–).22 Data are shown for dissociation into the ground state product channel. Previous measurements by Brouard and co-workers at 308 nm (solid circles),12 Zare and co-workers at 320 nm (open squares),10 and Bracker et al. at 355 nm (open triangles)9 are also shown.

Image of FIG. 9.
FIG. 9.

Only possible mechanism for a non-adiabatic transition leading to non-zero f 2(1, −1). Note that a similar mechanism can be drawn with the non-adiabatic transfer taking place from the C1Π1u Ω = −1 sub-state. This mechanism, however, would be associated with the f 2( − 1, 1) dynamical function, which is related to f 2(1, −1) by symmetry.39 Adapted from Ref. 9.

Image of FIG. 10.
FIG. 10.

Incoherent K = 1 and 3 orientation parameters returned from the fits to the Cl Fourier moments (open circles) and compared to theory (—–).22 Data are shown for dissociation into the ground state product channel. Previous measurements by Zare and coworkers (triangles)15 are also shown.

Image of FIG. 11.
FIG. 11.

Coherent η3 orientation parameter returned from the fits to the Cl Fourier moments (open circles) and compared to the recent theoretical study (—–).22 Data are shown for dissociation into the ground state product channel.

Image of FIG. 12.
FIG. 12.

Incoherent K = 2 alignment parameter returned from the fits to the Cl Fourier moments (open circles) and compared to theory (—–).22 Data are shown for dissociation into the excited state product channel. Previous measurements by Zare and coworkers (open squares)10 are also shown.

Image of FIG. 13.
FIG. 13.

Coherent K = 2 alignment parameter returned from the fits to the Cl Fourier moments (open circles) and compared to theory (—–).22 Data are shown for dissociation into the excited state product channel.

Image of FIG. 14.
FIG. 14.

Incoherent K = 1 and 3 orientation parameters returned from the fits to the Cl Fourier moments (open circles) and compared to theory (—–).22 Data are shown for dissociation into the excited state product channel.

Image of FIG. 15.
FIG. 15.

Coherent K = 1 and 3 orientation parameters returned from the fits to the Cl Fourier moments (open circles) and compared to the recent theoretical study (—–).22 The parameters γ1 and γ3 are shown in (a), while and are shown in (b). Data are shown for dissociation into the excited state product channel.

Image of FIG. 16.
FIG. 16.

parameter, multiplied by the factor [(2 − β)(1 + β)]1/2 for the Cl* fragments in the Cl + Cl* product channel. The solid black line represents the theoretical work described in the accompanying paper.22 The experimental data returned from fits to the Fourier moments of the ion images are represented by open circles, while the TOF REMPI data are shown as filled squares. Also shown is the parameter reported from the theoretical work by Asano and Yabushita17 for 35Cl* (black dashed) and 37Cl* (red dashed) fragments. Previous measurements by Zare and coworkers14 are represented by open triangles for 35Cl* (black) and 37Cl* (red). Note that the sign of the theoretical data has been inverted.

Tables

Generic image for table
Table I.

Spatial anisotropy and angular momentum polarization parameters for the Cl fragments from the ground state product channel returned from the fits to experimental data. Errors (1σ) in the last digit(s) are given in parenthesis.

Generic image for table
Table II.

Spatial anisotropy and angular momentum polarization parameters for the Cl fragments partnered by Cl* in the excited state product channel returned from the fits to experimental data. Errors (1σ) in the last digit(s) are given in parenthesis.

Generic image for table
Table III.

Spatial anisotropy and angular momentum polarization parameters for the Cl* fragments from the excited state product channel returned from the fits to experimental data. Errors (1σ) in the last digit(s) are given in parenthesis.

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/content/aip/journal/jcp/136/16/10.1063/1.4704830
2012-04-27
2014-04-19
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Electronic polarization effects in the photodissociation of Cl2
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/16/10.1063/1.4704830
10.1063/1.4704830
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