Unraveling Geometric-phase at Conical Intersection by Cavity-enhanced Two-dimensional Electronic Spectroscopy

Abstract: The geometric phase is a fundamental quantum mechanical phenomenon uniquely associated with conical intersections (CI) between potential energy surfaces and serves as a definitive signature of their presence. In this study, we propose a novel spectroscopic approach to directly detect the geometric phase using two-dimensional electronic spectroscopy (2DES) enhanced by strong light-matter interactions within an optical cavity. Focusing on a prototypical pentacene dimer undergoing singlet fission, we model the nonadiabatic wave packet dynamics as it evolves through a CI between electronically excited states. The optical cavity enables dynamic modulation of the coupling between the optical field and molecular vibrational modes, allowing precise control over the wave packet pathways. Importantly, we identify a cancellation in the spectral amplitude, arising from phase differences accumulated along different trajectories, which serves as a clear spectroscopic manifestation of the geometric phase (GP). This cavity-enhanced 2DES framework not only enables direct observation of GP effects but also offers a versatile platform for probing ultrafast nonadiabatic processes. Our results provide fundamental insights into topological effects in molecular dynamics and pave the way for experimental strategies in quantum control, photochemistry, and the design of advanced optoelectronic materials.