Dynamics of an excess electron at metal/polar interfaces

The low-temperature equilibrium and nonequilibrium solvation dynamics of an excess electron in bulk and at a surface interface have been characterized using mixed quanturn/classical simulation methods. A methanol bath was modeled using classical molecular dynamics, whereas the properties of an excess electron were calculated from a wave function based approach. The temperature dependence of the bulk response has been found to be minimal, which may indicate that large scale hydrogen bond breaking and diffusive motion may not play important roles in the solvation dynamics. The equilibrium dynamics have also been compared to nonequilibrium simulations of charge injection into the neat bath. An excess electron at a methanol/Pt(100) surface interface has been shown to become solvated by the bath yet is less bound by a factor of similar to2 compared to the bulk. The solvent response function also displays interesting differences when compared to the low temperature bulk glass. These results also reveal many of the microscopic properties of the solvated interfacial electrons that have recently been observed from ultrafast two photon photoelectron spectroscopy studies.