Probing Light-Induced Conical Intersections by Monitoring Multidimensional Polaritonic Surfaces

TL;DR

This paper demonstrates that ultrafast radiative emission monitoring can reveal nuclear dynamics and nonadiabatic transitions at light-induced conical intersections in molecules within nano-cavities, offering a new experimental fingerprint.

Contribution

It introduces a method to probe light-induced conical intersections through time-resolved emission, avoiding the need for additional probe pulses.

Findings

Ultrafast emission traces nuclear wavepacket dynamics.

Nonadiabatic transfer between polaritonic surfaces is observable.

Emission provides a clear fingerprint of conical intersections.

Abstract

The interaction of a molecule with the quantized electromagnetic field of a nano-cavity gives rise to light-induced conical intersections between polaritonic potential energy surfaces. We demonstrate for a realistic model of a polyatomic molecule that the time-resolved ultrafast radiative emission of the cavity enables to follow both nuclear wavepacket dynamics on and nonadiabatic population transfer between polaritonic surfaces without applying a probe pulse. The latter provides an unambiguous (and in principle experimentally accessible) dynamical fingerprint of light-induced conical intersections.