Optical Spectroscopy of the Bulk and Interfacial Hydrated
Electron from Ab Initio Calculations
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Abstract
The optical spectrum of the hydrated
(aqueous) electron, e<sub>aq</sub><sup>–</sup>, is the
primary observable by means of which this species is detected, monitored,
and studied. In theoretical calculations, this spectrum has most often
been simulated using one-electron models. Here, we present ab initio
simulations of that spectrum in both bulk water and, for the first
time, at the water/vapor interface, using density functional theory
and its time-dependent variant. Our results indicate that this approach
provides a reliable description, and quantitative agreement with the
experimental spectrum for the bulk species is obtained using a “tuned”
long-range corrected functional. The spectrum of the interfacial electron
is found to be very similar to the bulk spectrum