Potential-energy curves for the , , , , , , , and states of SH. The vibrational levels of the state are labeled. The information is adapted from Refs. 5–7. The arrow in the figure represents the energy of a photon.
H-atom TOF spectrum of photodissociation of SH and , with the photolysis laser for radical production on and off. The polarization vector of the 226-photodissociation radiation is perpendicular to the TOF axis. The spectrum in short-dashed line is with radiation off, i.e., a simple TOF spectrum of jet-cooled at (in region); the weak broad feature in region is due to secondary photolysis of the SH radical produced from photolysis of . The spectrum in solid line is with radiation on, with the similar and SH signals from the slightly depleted precursors and, in addition, the three sharp peaks around from photodissociation of jet-cooled SH radicals in the beam.
Center-of-mass product translational energy distribution from photodissociation of SH, with polarization vector of the photolysis radiation perpendicular and parallel to the TOF axis. The spin-orbit sublevels of the products are labeled.
Anisotropy parameter vs photolysis wavelengths. The parameter stays very close to the limit of a pure perpendicular transition. The error bar at represents 95% confidence limit and is assumed be the same for the values at other wavelengths. The dashed line is the limit of a prompt dissociation from a perpendicular transition.
Examples of CM product translational energy distributions ’s of UV photodissociation of SH, with polarization of the photolysis radiation perpendicular to the TOF axis. The spin-orbit sublevels of the products are deconvoluted by fitting with slightly asymmetric Gaussian peaks and are shown in the figure (see the text for details). (a) Photodissociation of at and (b) photodissociation of at .
(a) Spin-orbit branching fractions of the product vs photolysis wavelengths in the photodissociation of . The error bars represent 95% confidence limit. The sudden limit branching fractions of the three product channels are 0.556:0.333:0.111 and are shown by the straight lines. The spin-orbit branching fractions at by Ashfold and co-workers are shown by the filled symbols. (b) Spin-orbit branching fractions of the product vs photolysis wavelengths in the photodissociation of . The error bar represents 95% confidence limit.
Correlation diagram connecting the ground and three repulsive electronic excited states of SH with the separated atom product states . is the projection of the total electronic angular momentum along the internuclear axis and is conserved in the dissociation process between the molecular and atomic states. See Refs. 43 and 44 for more information.
spin-orbit branching fractions and anisotropy parameter of photodissociation of at the UV photolysis wavelength range of . The errors in the spin-orbit branching fractions in the photodissociation of in are 95% confidence limit, and the 95% confidence limit for the values is . The errors in the photodissociation of in and 2 are larger due to the weaker signals.
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