Note: Deep UV-pump THz-probe spectroscopy of the excess electron in water

Abstract

In the work of Savolainen et al. [Nat. Chem. 6, 697 (2014)], we studied the excess (hydrated) electron in water with the help of transient THz spectroscopy, which is a sensitive probe of its delocalization length. In that work, we used laser pulses at 800 nm, 400 nm, and 267 nm for photoionization. While the detachment mechanism for 400 nm and 267 nm is complicated and requires a concerted nuclear rearrangement, we provided evidence that 800 nm pumping excites the excess electron directly and vertically into the conduction band, despite a highly nonlinear field-ionization process. In the present note, we extend that work to 200 nm pumping, which provides a much cleaner way to reach the conduction band. We show that the detachment pathways upon 200 nm and 800 nm pumping are in essence the same, as indicated by the same initial size of the electron wavefunction and the same time scales for the collapse of the wavefunction and geminate recombination.