Probing the Interstate Coupling near a Conical Intersection by Optical Spectroscopy.

Conical intersections are points where adiabatic potential energy surfaces cross. The interstate coupling between the potential energy surfaces plays a crucial role in many processes associated with conical intersections. Still no method exists to measure this coupling driving the chemical reactions between the potential energy surfaces involved. In this Letter, using a generic model for photoisomerization, we propose a novel experimental approach to estimate the coupling that mixes the electronic states near a conical intersection. The approach is based on analyzing the vibrational wavepacket of the reactant in the adiabatic ground and excited electronic states. The nuclear wavepacket dynamics are extracted from linear absorption and two-dimensional electronic spectroscopy. Comparing the frequencies of the coupling mode in the adiabatic ground and excited states from models with and without coupling between the potential energy surfaces suggests an experimental tool to determine the interstate coupling.