Conical Intersection versus Avoided Crossing: Geometric Phase Effect in Molecular High-Order Harmonics

Abstract

Nonadiabatic dynamics around an avoided crossing or a conical intersection play a crucial role in the photoinduced processes of most polyatomic molecules. The present work shows that the topological phase in conical intersection makes the behavior of pump-probe high-order harmonic signals different from the case of avoided crossing. The coherence built up when the system crosses the avoided crossing will lead to the oscillatory behavior of the spectrum, while the geometric phase erodes these oscillations in the case of conical intersection. Additionally, the dynamical blueshift and the splitting of the time-resolved spectrum allow capturing the snapshot dynamics with the sub-femtosecond resolution.