Controlling molecular ground-state dissociation by optimizing vibrational ladder climbing

To achieve large population transfer to high vibrational levels in a selected ground-state mode of a polyatomic molecule $[\mathrm{Cr}(\mathrm{CO}{)}_6\mathrm{],}$ we apply chirped femtosecond mid-infrared laser pulses at $\text{2000\hspace{0.17em}}{\mathrm{cm}}^{\text{−1}}$ to optimize vibrational ladder climbing as an energy deposition mechanism, which in turn controls the outcome of a unimolecular dissociation process. Its dependence on excitation parameters (frequency, intensity, chirp) is investigated and found to be in excellent agreement with a theoretical calculation. In particular, it is shown that optimizing vibrational ladder climbing allows for coherently controlled excitation even in a polyatomic molecule.