Simulation of volume polarization in reaction field theory

Abstract

Articles you may be interested inHow to measure a complete set of polarization-dependent differential cross sections in a scattering experiment with aligned reagents?In the reaction field theory of solvation, penetration of charge density outside the cavity nominally enclosing the solute leads to a volume polarization that contributes in addition to the commonly recognized surface polarization. In principle the exact volume polarization charge density is spread everywhere outside the cavity, but its effect can be closely and concisely simulated by a certain additional surface polarization charge density. Formal comparison is made to conductorlike screening models, and it is found that these improve on common approaches that neglect volume polarization by automatically including the simulation of volume polarization. A revised method to numerically determine this simulation is also described.

A variational formulation of the polarizable continuum model

“…͑30͒ is more convenient because the PCM linear system is a symmetric one. 32,37 Other authors 34,38 choose Eq. ͑28͒ because it naturally goes to the right limit for → ϱ, i.e.,…”

Boundary element methods for dielectric cavity construction and integration

“…The nature of the empirical parameter used 16,22,45 by several workers to improve convergence can be illustrated by considering the potential produced by a net unit charge distributed uniformly over the surface of a sphere ⌫ having radius s. The surface charge density then has a constant value of 1/4s 2 everywhere on ⌫. The electrostatic potential at an arbitrary surface point, say s q , can be easily worked out analytically to obtain 1…”

“…Singular integrands associated with evaluating the electrostatic potential on the cavity surface particularly hinder convergence of recent methods such as COSMO 16 ͑conductor screening model͒, the current modification of IEF-PCM 43,44 ͑integral equation formulation of the polarized continuum model͒, and SS͑V͒PE 45,46 ͑surface and simulation of volume polarization for electrostatics͒ that reliably incorporate into the surface charge density some representation of the important influences of volume polarization effects arising from solute charge penetration outside the cavity.…”

An efficient implementation for determining volume polarization in self-consistent reaction field theory

“…In recent studies 11,12,[19][20][21] the direct volume polarization is simulated as an additional surface polarization charge distribution on the cavity surface in order to reduce the computational cost. Such an approximate method is known as the SS͑V͒PE method.…”

“…The simulation approach is known as the surface and simulated volume polarizations for electrostatics ͓SS͑V͒PE͔ method. 11 Recently reported formal analyses 11,12 of the simulation have also demonstrated that in the limit of infinite dielectric constant, the simulation of volume polarization effects is automatically included in the integral equation formulation of polarizable continuum model ͑IEFPCM͒ ͑Ref. 13͒ and the conductorlike screening model ͑COSMO͒.…”