Electronic states at the water/air interface.
Using combined path integral-molecular dynamics simulation techniques, we analyze electronic solvation at the water/air interface. Superficial electrons present a considerable extent of spatial confinement, somewhat less marked but still comparable to that found in bulk. The characteristics of the interfacial polarization promote an overall structure for the solvated electron-polymer which looks flatter along the direction perpendicular to the interface. Spatial and orientational responses of different slabs in the close vicinity of the interface were also investigated. Solvent configurations obtained from the simulations have been used to analyze electronic excited states and the optical absorption spectrum of superficial electrons. Compared to bulk results, the distribution of bound electronic states at the surface presents similar characteristics, that is, a ground s-state and three, quasi-degenerate, p-like excited states. The reduction of the energy gap between the ground state and the rest of excited states leads to a approximately 0.52 eV red-shift in the position of the absorption maximum.
Rodriguez
Javier
J
Unidad Actividad Química, Comisión Nacional de Energía Atómica, Avenida Libertador 8250, 1429 Buenos Aires, Argentina.
Laria
Daniel
D