Coherent nonlinear optical probe for cavity-dressed vibrational mode mixing: Multidimensional double-quantum coherence and photon-echo spectroscopy

Cavity dressing of molecular vibrational dynamics expands the role of characteristic vibrations as spectroscopic markers of underlying ultrafast dynamics.

Interacting vibrational modes exhibit a pronounced excited state delocalization due to the interaction with the cavity mode, which is reflected in the ultrafast dynamics.

We characterize the ultrafast dynamics of these cavity-dressed characteristic vibrations in the presence of dissipation.

Specifically, we present two complementary three-pulse coherent multidimensional spectroscopic techniques capable of monitoring one- and two-quantum cavity-dressed vibrational excitations.

Dissipative properties, such as transport and dephasing, are described using a microscopic theory that includes low- and high-energy phonon modes.

Simulations were performed with finite laser pulses.

The cavity coupling strengths fall within a range similar to vibrational mode couplings, hinting towards a possibility of control of intermolecular vibrational energy redistribution.

The framework is extendable to a broad range of cavity-controlled nonlinear spectroscopies of dissipative molecular systems.