Multidimensional semiclassical single- and double-quantum spectroscopy of anharmonic molecular polaritons

TL;DR

This paper introduces a semiclassical method for computing phase-resolved multidimensional spectra of anharmonic molecular polaritons, enabling detailed analysis of nonlinear optical signals in strongly coupled light-matter systems.

Contribution

The authors develop a systematic, computationally simple approach to generate phase-cycled two-dimensional polariton spectra, bridging theory with experimental observations and insights into anharmonic effects.

Findings

Successfully benchmarked against experimental spectra, explaining the polariton bleach effect.

Demonstrated the ability to probe anharmonicities in the double-excitation manifold.

Provided a framework for modeling and interpreting nonlinear spectroscopic experiments.

Abstract

We present a general and efficient approach to compute phase-resolved multidimensional spectra of anharmonic molecular polaritons, based on a semiclassical evolution of the molecular Hamiltonian and cavity field in the large-$\mathcal{N}$ limit of many molecules coupled to a confined photonic mode. By systematically expanding the response in both amplitudes and phases of the input fields, our method enables a transparent and computationally simple construction of phase-cycled two-dimensional single- and double-quantum polariton spectra from the underlying nonlinear signal components. Here, phase cycling acts as an analogue of phase matching with oblique pulses, allowing for the isolation of the contributing nonlinear pathways in Liouville space. We specialize to vibrational polaritons and benchmark the method through direct comparison with experimentally measured single-quantum spectra, providing an explanation for the longstanding puzzle of the polariton bleach effect observed at short waiting times. Further, we show how the imprint of various types of anharmonicities on the double-excitation manifold can be directly probed and analyzed through double-quantum coherence spectroscopy. Taken together, our results establish a practical and powerful framework for the modeling and interpretation of nonlinear spectroscopic experiments on strongly coupled light-matter platforms and for guiding the design of cavity-enhanced molecular platforms.