The static-exchange electron-water pseudopotential, in conjunction with a polarizable water model: a new Hamiltonian for hydrated-electron simulations

• Published in: The Journal of chemical physics Vol. 130; no. 12; p. 124115
• Main Authors: Jacobson, Leif D, Williams, Christopher F, Herbert, John M
• Format: Journal Article
• Language: English
• Published: United States 28.03.2009
• ISSN: 1089-7690
• DOI: 10.1063/1.3089425

Previously, Turi and Borgis [J. Chem. Phys. 117, 6186 (2002)] parametrized an electron-water interaction potential, intended for use in simulations of hydrated electrons, by considering H(2)O(-) in the "static exchange" (essentially, frozen-core Hartree-Fock) approximation, then applying an approximate Phillips-Kleinman procedure to construct a one-electron pseudopotential representing the electron-water interaction. To date, this pseudopotential has been used exclusively in conjunction with a simple point charge water model that is parametrized for bulk water and yields poor results for small, neutral water clusters. Here, we extend upon the work of Turi and Borgis by reparametrizing the electron-water pseudopotential for use with the AMOEBA water model, which performs well for neutral clusters. The result is a one-electron model Hamiltonian for (H(2)O)(n)(-), in which the one-electron wave function polarizes the water molecules, and vice versa, in a fully self-consistent fashion. The new model is fully variational and analytic energy gradients are available. We have implemented the new model using a modified Davidson algorithm to compute eigenstates, with the unpaired electron represented on a real-space grid. Comparison to ab initio electronic structure calculations for (H(2)O)(n)(-) cluster isomers ranging from n=2 to n=35 reveals that the new model is significantly more accurate than the Turi-Borgis model, for both relative isomer energies and for vertical electron detachment energies. Electron-water polarization interactions are found to be much more significant for cavity states of the unpaired electron than for surface states.