A Simple ab Initio Model for the Solvated Electron in Methanol.
The solvation structure of a solvated electron in methanol is investigated with ab initio calculations of small anion methanol clusters in a polarized dielectric continuum. We find that the lowest-energy structure in best agreement with experiment, calculated with CCSD, MP2, and B3LYP methods with aug-cc-pvdz basis set, is a tetrahedral arrangement of four methanol molecules with OH bonds oriented toward the center. The optimum distance from the tetrahedron center to the hydroxyl protons is ∼1.8 Å, significantly smaller than previous estimates. We are able to reproduce experimental radius of gyration Rg (deduced from optical absorption), vertical detachment energy, and resonance Raman frequencies. The electron paramagnetic resonance g-factor shift is qualitatively reproduced using density functional theory.
Radiation Laboratory and Dept. of Chemistry & Biochemistry, Notre Dame University , Notre Dame, Indiana 46556, United States.
J A
JA
Walker
Radiation Laboratory and Dept. of Chemistry & Biochemistry, Notre Dame University , Notre Dame, Indiana 46556, United States.
D M
DM
Bartels