Electron at the Surface of Water: Dehydrated or Not?
The hydrated electron is a crucial species in radiative processes, and it has been speculated that its behavior at the water surface could lead to specific interfacial chemical properties. Here, we address fundamental questions concerning the structure and energetics of an electron at the surface of water. We use the method of ab initio molecular dynamics, which was shown to provide a faithful description of solvated electrons in large water clusters and in bulk water. The present results clearly demonstrate that the surface electron is mostly buried in the interfacial water layer, with only about 10 % of its density protruding into the vapor phase. Consequently, it has a structure that is very similar to that of an electron solvated in the aqueous bulk. This points to a general feature of charges at the surface of water, namely, that they do not behave as half-dehydrated but rather as almost fully hydrated species.
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, CZ-16610 Prague 6, Czech Republic.
Frank
F
Uhlig
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, CZ-16610 Prague 6, Czech Republic.
Ondrej
O
Marsalek
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, CZ-16610 Prague 6, Czech Republic.
Pavel
P
Jungwirth
DFT; QM/MM; air/water interface; hydrated electron; ionization potentials; photoionization; water