Electron confinement within a fluctuation "box" in liquid water

TL;DR

This study investigates hydrated electrons in liquid water, revealing their highly fluctuating, nonuniform confinement within transient cavities, which differs fundamentally from solid-state electron confinement.

Contribution

It provides experimental evidence of the dynamic and nonuniform nature of electron confinement in liquid water using advanced spectroscopy.

Findings

Hydrated electrons exhibit significant shape and size fluctuations.

Confinement occurs within transient, flexible cavities in water.

Fluctuations happen on sub-30 femtosecond timescales.

Abstract

Electron confinement within a small volume is intriguing as a realization of the particle-in-a-box system, which appears in every quantum mechanics textbook. While the electron confinement is readily imaginable in solid-state systems, it also occurs in liquids, where the local voids in the liquid serve as confining "boxes." Confinement within these flexible cavities in liquids is expected to differ fundamentally from that in solids. Here, we experimentally investigate the electrons confined in liquid water, which are called hydrated electrons, using transient two-dimensional electronic spectroscopy. Our experiment reveals the large nonuniformity of the shape and the size of hydrated electrons with significant fluctuation at the timescale shorter than 30 fs.