Uniform electrostatic perturbation

Section 12-3 A Uniform Electrostatic Perturbation of an Electron in a Wire ... 

Rao and Singh32 calculated relative solvation free energies for normal alkanes, tetra-alkylmethanes, amines and aromatic compounds using AMBER 3.1. Each system was solvated with 216 TIP3P water molecules. The atomic charges were uniformly scaled down by a factor of 0.87 to correct the overestimation of dipole moment by 6-31G basis set. During the perturbation runs, the periodic boundary conditions were applied only for solute-solvent and solvent-solvent interactions with a non-bonded interaction cutoff of 8.5 A. All solute-solute non-bonded interactions were included. Electrostatic decoupling was applied where electrostatic run was completed in 21 windows. Each window included 1 ps of equilibration and 1 ps of data... 

Across real surfaces and interfaces, the dielectric response varies smoothly with location. For a planar interface normal to a direction z, we can speak of a continuously changing s(z). More pertinent to the interaction of bodies in solutions, solutes will distribute nonuniformly in the vicinity of a material interface. If that interface is charged and the medium is a salt solution, then positive and negative ions will be pushed and pulled into the different distributions of an electrostatic double layer. We know that solutes visibly change the index of refraction that determines the optical-frequency contribution to the charge-fluctuation force. The nonuniform distribution of solutes thereby creates a non-uniform e(z) near the interfaces of a solution with suspended colloids or macromolecules. Conversely, the distribution of solutes can be expected to be perturbed by the very charge-fluctuation forces that they perturb through an e(z).5... 

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