Optical spectroscopy of the bulk and interfacial hydrated electron from ab initio calculations
Research output: Contribution to journal › Article › Scientific › peer-review
|Number of pages||9|
|Journal||Journal of Physical Chemistry A|
|Publication status||Published - 4 Sep 2014|
|Publication type||A1 Journal article-refereed|
The optical spectrum of the hydrated (aqueous) electron, eaq -, 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. (Figure Presented).