Mones, Letif and Turi, László (2010) A new electron-methanol molecule pseudopotential and its application for the solvated electron in methanol. Journal of Chemical Physics, 132 (15). p. 154507. ISSN 1089-7690
A new electron–methanol molecule pseudopotential is developed and tested in the present paper. The formal development of the potential is based on quantum mechanical calculations on the electron-methanol molecule model in the static exchange approximation. The computational model includes a steep confining potential that keeps the otherwise unbound excess electron in the vicinity of the methanol molecule. Using the Phillips-Kleinman theorem we introduce a smooth pseudo-wave function of the excess electron with the exact eigenenergy and correct asymptotic behavior. The non-local potential energy operator of the model Hamiltonian is then replaced to a local potential that reproduces the ground-state properties of the excess electron satisfactorily. The pseudopotential is then optimized in an analytically simple functional form to fit this approximate local potential in conjunction with the point charges and the geometry of a classical, all-site methanol-methanol interaction potential. Of the adjustable parameters, the parameters for the carbon and the methyl hydrogen atoms are optimized, while those for the oxygen and the hydroxyl hydrogen are taken from a previous electron-water molecule pseudopotential. A polarization term is added to the potential a posteriori. The polarization parameters are chosen to reproduce the experimental position of the optical absorption spectrum of an excess electron in mixed quantum-classical molecular dynamics simulations. The energetic, structural and spectroscopic properties of the solvated electron in a methanol bath are simulated at 300 K, and compared to previous solvated electron simulations and available experimental data.
|Subjects:||Q Science / természettudomány > QD Chemistry / kémia > QD02 Physical chemistry / fizikai kémia|
|Depositing User:||Dr. Túri László|
|Date Deposited:||16 Apr 2012 07:21|
|Last Modified:||03 Sep 2012 13:19|
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