화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.120, No.36, 7240-7247, 2016
A Simple ab lnitio 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 similar to 1.8 angstrom, significantly smaller than previous estimates. We are able to reproduce experimental radius of gyration R-g (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.