Vibrational dynamics of ions in glass from fifth-order two-dimensional infrared spectroscopy

The vibrational dynamics of the first four antisymmetric stretch vibrational levels of azide in an ionic glass have been measured and correlated using a heterodyned fifth-order two-dimensional infrared pulse sequence. By rephasing a two-quantum coherence, a process not possible with third-order spectroscopy, solvent effects on the frequencies and anharmonicities of the potential energy surface are measured. Fifth-order pulse sequences are another step towards precisely controlling vibrational coherence in analogy to the manipulation of spins in NMR but with ultrafast time resolution.