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The photodissociation dynamics of ozone at 226 and : atomic angular momentum polarization
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10.1063/1.2790890
/content/aip/journal/jcp/127/14/10.1063/1.2790890
http://aip.metastore.ingenta.com/content/aip/journal/jcp/127/14/10.1063/1.2790890

Figures

Image of FIG. 1.
FIG. 1.

Cut through the lowest five surfaces for ozone adapted from Ref. 69 with one O-O distance fixed at and the bond angle at its ground state equilibrium value of 117°. Potentials are labeled according to the notation of Hay et al. (Ref. 6). Relative energy ordering of the spin-orbit states is also shown. Top right panel: Singlet, triplet, and quintet molecular states of and symmetries as a function of one O–O bond distance, with other coordinates fixed at their ground state equilibrium values. Adapted from Ref. 36.

Image of FIG. 2.
FIG. 2.

(Color) Dissociation wavelength, . Images, Fourier moments (—), and fits (---) for products. Pump-probe geometries, from top to bottom: HH, HV, VH, and VV. Nonzero experimental and fitted moments are shown in gray.

Image of FIG. 3.
FIG. 3.

(Color) Dissociation wavelength, . Images, Fourier moments (—), and fits (---) for (top) products in the HH pump-probe geometry, (middle) products, and (bottom) products dissociated with polarized photolysis light. The last two images and Fourier moments shown are the differences between sets of data collected with left- and right-circularly polarized probe light. Positive and negative intensity portions of the images have been marked. Nonzero experimental and fitted moments are shown in gray. The spacing of the abscissa marks on the last two panels correspond to one-tenth of the spacing of the abscissa marks on the top panel.

Image of FIG. 4.
FIG. 4.

Dissociation wavelength, . Speed distributions and parameters for (top to bottom) , , and . A comb for the vibrational state of in the absence of rotational excitation is shown in the top left panel. Errors represent a confidence limit. The separation between fast and slow regimes is marked with a vertical dotted line.

Image of FIG. 5.
FIG. 5.

Dissociation wavelength, . Speed distributions and parameters for (top to bottom) , , and . A comb for the vibrational state of in the absence of rotational excitation is shown in the top left panel. Errors represent a confidence limit. The separation between fast and slow regimes is marked with a vertical dotted line.

Image of FIG. 6.
FIG. 6.

Dissociation wavelength, . Speed dependent angular momentum alignment and orientation parameters following dissociation at for (—) and (---). All parameters not displayed here were found to be zero within experimental confidence limits. Error bars indicate confidence limit. The separation between fast and slow regimes is marked with a vertical dotted line.

Image of FIG. 7.
FIG. 7.

Bottom left: Example raw data (∙∙∙) and fit (—) to the internal energy distribution of the cofragments of generated from the photodissociation of ozone at . Refer to text for details of the simulations. Top panel: vibrational state populations recovered from fits to the speed distributions for dissociation at for (—), (---), and (gray solid line). Bottom right panel: As for the top panel but for dissociation at . In all fits, the rotational distributions were modeled using a Gaussian function peaking at with a width of of angular momentum.25 Average errors of around 25% are associated with the reported populations. Vibrational populations from the work of Miller et al. (Ref. 10) are shown in the bottom right panel as filled circles.

Image of FIG. 8.
FIG. 8.

Adiabatic, -conserving correlation diagram for dissociation of ozone to ground state products at linear configurations. The ordering of the molecular states is taken from the work of Rosmus et al. (Ref. 36). The energy ordering of the states and of the states has been established on the basis of Hund’s rules. Different line styles have been used to facilitate the reading of the correlations. The molecular state has components, which arise from different combinations of the projections of the spin quantum numbers from atomic and molecular entities.

Image of FIG. 9.
FIG. 9.

Dissociation wavelength, . Molecular frame -state multipoles for slow and fast and fragments calculated using the equations in Sec. II B. Symbols represent (-∙∙-), (—), (∙∙∙), and (---). Maximum errors of approximately 50% are associated with state multipoles for products, while a maximum of 15% with multipoles.

Image of FIG. 10.
FIG. 10.

Dissociation wavelength, . Top panels: Scattering angle averaged populations for (left) and (right) products. Populations corresponding to slow (white) and fast (gray) products have been plotted separately. Bottom panels: Molecular frame -state multipoles for fast fragments calculated using the spin-polarized fast dissociation model. See text for details. Symbols represent (-∙∙-), (—), (∙∙∙), and (---).

Image of FIG. 11.
FIG. 11.

Long-range interaction potentials and predicted state multipoles. See text for details. Symbols represent (—), (∙∙∙), and (---).

Tables

Generic image for table
Table I.

Speed averaged spatial anisotropy and polarization parameters for fragments following dissociation at 248 and . errors reported refer to the last digit(s) shown. and orientation parameters were found to be zero at . The limiting values for the polarization parameters have been given in Ref. 76, with those for the alignment moments reproduced in Ref. 41. The measured values of the parameters are typically at least five to ten times smaller than the limiting values.

Generic image for table
Table II.

Spatial anisotropy parameters averaged over fast and slow speed regimes for fragments at a series of wavelengths. The fraction of slow products formed is also given.

Generic image for table
Table III.

atomic angular momentum polarization parameters for the fast and slow photofragments subsequent to dissociation at . errors reported refer to the last digit(s) shown. The limiting values for the polarization parameters have been given in Ref. 76, with those for the alignment moments reproduced in Ref. 41. The measured values of the parameters are typically at least five to ten times smaller than the limiting values.

Generic image for table
Table IV.

Scattering angle averaged orbital/spin angular momentum state multipoles computed using the spin-polarized fast dissociation model. Errors represent a confidence limit.

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/content/aip/journal/jcp/127/14/10.1063/1.2790890
2007-10-08
2014-04-19
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: The photodissociation dynamics of ozone at 226 and 248nm: O(PJ3) atomic angular momentum polarization
http://aip.metastore.ingenta.com/content/aip/journal/jcp/127/14/10.1063/1.2790890
10.1063/1.2790890
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