Optical Spectroscopy of the Bulk and Interfacial Hydrated Electron from Ab Initio Calculations.

The journal of physical chemistry. A

PubMedID: 24576141

Uhlig F, Herbert JM, Coons MP, Jungwirth P. Optical Spectroscopy of the Bulk and Interfacial Hydrated Electron from Ab Initio Calculations. J Phys Chem A. 2014;.
The optical spectrum of the hydrated (aqueous) electron, e-aq, 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 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.