A quantum molecular dynamics simulation of an excess electron in methanol

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Abstract
The structure, energetics, and dynamics of a ground‐state, excess electron in the polar solvent methanol are simulated. Two pseudopotentials describing the interaction of the excess electron and the methanol molecules are developed. An adiabatic simulation method is used whereby the Schrödinger equation for the electron is solved in the presence of a fixed solvent configuration and the solvent configuration is advanced with the forces arising from the methanol interactions and the expectation value of the electron–methanol interaction. We find that the electron is localized with average radii of 3.1 and 2.6 Å, depending on which pseudopotential is used, and both show a fairly strong solvation structure. The methanols are on average methoxyl bond‐dipole oriented toward the electron in one model and hydroxyl bond‐dipole ordered in the other. The binding energy (kinetic plus potential) of the electron fluctuates about the value −2.2 eV. The electron solvates on about a 400 fs time scale with a fast decay component of ∼30 fs. The dynamics of the electron’s center of mass can be described by a diffusion process with a diffusion constant ≂1.9×10−5 cm2 s−1.

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