  We report the first experimental two-dimensional infrared (2D IR) spectra of
novel molecular photonic excitations - vibrational-polaritons. The application
of advanced 2D IR spectroscopy onto novel vibrational-polariton challenges and
advances our understanding in both fields. From spectroscopy aspect, 2D IR
spectra of polaritons differ drastically from free uncoupled molecules; from
vibrational-polariton aspects, 2D IR uniquely resolves hybrid light-matter
polariton excitations and unexpected dark states in a state-selective manner
and revealed hidden interactions between them. Moreover, 2D IR signals
highlight the role of vibrational anharmonicities in generating non-linear
signals. To further advance our knowledge on 2D IR of vibrational polaritons,
we develop a new quantum-mechanical model incorporating the effects of both
nuclear and electrical anharmonicities on vibrational-polaritons and their 2D
IR signals. This work reveals polariton physics that is difficult or impossible
to probe with traditional linear spectroscopy and lays the foundation for
investigating new non-linear optics and chemistry of molecular
vibrational-polaritons.
