Two-color optical-optical double resonance (OODR) probe of the , or , states via successive excitation to the , state of jet-cooled thiophosgene. In this experiment, the frequency sum of the pump laser and probe laser was locked during scanning , so that vibronic resonances of the or state were interrogated through the ultraviolet fluorescence from the same monitor vibronic level.
A comparison of the vibronic structure of the and states through (a) the and (b) OODR processes.
The spectra associated with the , , and vibrational blocks. (a) The block: , (b) , and (c) the block obtained from the OODR processes in jet-cooled thiophosgene. Wave numbers are relative to (a) the origin band , (b) band , and (c) band .
Detailed comparisons of the inversion splitting pair of (a) the ( and ), (b) ( and ), and (c) ( and ) levels in the state of thiophosgene probed via the ( or ) OODR processes. The lower trace of each panel is shifted by .
The calculated and observed spectra for the spin component of the transition in thiophosgene. The constants of Table III have been used in generating the calculated spectra.
The (origin) band of the jet-cooled thiophosgene with (a) the low-resolution and (b) high-resolution scans via the OODR process, indicating the existence of the spin sublevels at the red side of the intense spin component.
The calculated and observed spectra of the isotopomer for the and spin components of the transition in thiophosgene. The constants of the spin component were used in generating the spectrum. The transition moments of the and were set to 100% and that of the spin state was set to 10%.
(Color online) Temporal profiles of the fluorescence from the level, prepared via OODR as functions of time delay and spatial displacement between the pump-probe lasers. Panel (a) shows the long trail contour of that indicates a long-lived state. Panel (b) shows the measurement with a short time range and reveals the presence of a nanosecond decay component. Inset: Schematic pump-probe laser configuration including a molecular jet (see the text for details).
Comparison of (a) the OODR, (b) laser-induced phosphorescence (LIP), and (c) one-color OODR spectra of jet-cooled thiophosgene recorded with strong laser-power input. The asterisks in the LIP (LIF) spectrum show very weak phosphorescence bands originating from the direct one-color, one-photon excitation.
Observed band heads in the [manifold of species from ; wave number accuracy of ], [manifold of species from , attached , , or ; wave number accuracy of ], and [manifold of species from , attached ; wave number accuracy of ] OODR spectra of (in ).
Observed and calculated energy levels (in ). Potential and kinetic energy parameters (in rad and ).
Values of the various parameters used in simulating the band contours (Figs. 5 and 7). The values quoted in parentheses are the standard deviation for the constants varied in the least-squares fit.
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