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

Abstract

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.