Franck-Condon fingerprinting of vibration-tunneling spectra.

We introduce Franck-Condon fingerprinting as a method for assigning complex vibration-tunneling spectra. The B̃ state of thiophosgene (SCCl2) serves as our prototype. Despite several attempts, assignment of its excitation spectrum has proved difficult because of near-degenerate vibrational frequencies, Fermi resonance between the C-Cl stretching mode and the Cl-C-Cl bending mode, and large tunneling splittings due to the out-of-plane umbrella mode. Hence, the spectrum has never been fitted to an effective Hamiltonian. Our assignment approach replaces precise frequency information with intensity information, eliminating the need for double resonance spectroscopy or combination differences, neither of which have yielded a full assignment thus far. The dispersed fluorescence spectrum of each unknown vibration-tunneling state images its character onto known vibrational progressions in the ground state. By using this Franck-Condon fingerprint, we were able to determine the predominant character of several vibration-tunneling states and assign them; in other cases, the fingerprinting revealed that the states are strongly mixed and cannot be characterized with a simple normal mode assignment. The assigned transitions from vibration-tunneling wave functions that were not too strongly mixed could be fitted within measurement uncertainty by an effective vibration-tunneling Hamiltonian. A fit of all observed vibration-tunneling states will require a full resonance-tunneling Hamiltonian.