Multi-plateau high-harmonic generation in liquids driven by off-site recombination

Abstract

Non-perturbative high-harmonic generation (HHG) has recently been observed in the liquid phase, where it was demonstrated to have a different physical mechanism compared to gas and solid phases of matter. The currently best physical picture for liquid HHG eliminates scattered-electron contributions and identifies on-site recombination as the dominant contributor. This mechanism accurately predicts the cut-off energy and its independence of the driving laser wavelength and intensity. However, this implies that additional energy absorbed in the liquid as the driving laser intensity is increased does not result in higher-order non-linearities, which is in contrast to the conventional expectation from most nonlinear media. Here we experimentally observe the formation of a second plateau in HHG from multiple liquids (water, heavy water, propranol, and ethanol), thus explaining the conundrum of the missing higher-order response. We analyze this second plateau with a combination of experimental, state-of-the-art ab-initio numerical (in diverse systems of water, ammonia, and liquid methane), and semi-classical analytical, techniques, and elucidate its physical origin to electrons that recombine on neighboring water molecules rather than at the ionization site, leading to unique HHG ellipticity dependence. Remarkably, we find that the second plateau is dominated by electrons recombining at the second solvation shell, relying on wide hole delocalization. Theory also predicts the appearance of even higher plateaus, indicating a general trend. Our work establishes new physical phenomena in the highly non-linear optical response of liquids, paving the way to attosecond probing of electron dynamics in solutions.