The over(X, ∼) ← over(A, ∼) SEP spectra of jet-cooled thiophosgene

Over 400 over(X, ∼) ← over(A, ∼) transitions of SCCl₂ have been measured by stimulated emission pumping from 209 to 240 THz above the over(X, ∼) state zero point. The over(A, ∼) state provides access to over 100 previously unassigned over(X, ∼) state vibrational levels. The vibrational manifold of SCCl₂ now has been mapped to maximum quanta in all six modes of (15, 4, 5, 18, 2, 2), providing a global view of vibrational dynamics. We report anharmonic constants that fit all currently available assigned vibrational energy levels. The onset of free energy flow has not been reached at E/h = 240 THz for states sampled here, in accordance with over(B, ∼) state SEP data and a theoretical analysis.