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Boundary integral methods for the Poisson equation of continuum dielectric solvation models
Author(s) -
Pratt Lawrence R.,
Tawa Gregory J.,
Hummer Gerhard,
García Angel E.,
Corcelli Steven A.
Publication year - 1997
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1997)64:1<121::aid-qua12>3.0.co;2-e
Subject(s) - solvation , dielectric , poisson's equation , integral equation , boundary value problem , statistical physics , multigrid method , boundary element method , implicit solvation , boundary (topology) , poisson distribution , chemistry , thermodynamics , physics , partial differential equation , ion , mathematical analysis , mathematics , finite element method , quantum mechanics , statistics
This article tests a dielectric model for the variation ofhydration free energy with the geometry of complex solutes in water. Itreexpresses the Poisson equation of the model to examine the basic aspectsof boundary integral methods for these problems. It compares eight examplesof dielectric model potentials of mean force in water with numericalresults obtained from molecular scale models by simulation. Instructive andphysical results are obtained but the model overstabilizes attractive,ion‐pairing configurations. The article describes the algorithms,alternative to those in the literature, used here for high‐precisionsolutions of that Poisson equation. Anticipating multigrid boundaryintegral approaches for similarly accurate treatment of larger solutioncomplexes, the adaptation of spatial resolution is discussed. Finally, thestatistical mechanical theory of the model is discussed together with a newproposal for describing the molecular detail of the solvation properties:integrating‐out a probe solvent molecule using the dielectric model. Theappendices give formal results relevant to periodic boundary conditions andinfinite area surfaces such as solution interfaces andmembranes. © 1997 John Wiley & Sons, Inc. Int J Quant Chem 64 : 121–141, 1997