Limitations of atom-centered dielectric functions in implicit solvent models.
Many recent advances in Poisson-Boltzmann and generalized Born implicit solvent models have used atom-centered polynomial or Gaussian functions to define the boundary separating low and high dielectric regions. In contrast to the Lee and Richards molecular surface, atom-centered surfaces result in interatomic crevices and buried pockets of high dielectric which are too small for a solvent molecule to occupy. We show that these interstitial high dielectric regions are of significant magnitude in globular proteins, that they artificially increase solvation energies, and that they distort the free energy surface of nonbonded interactions. These results suggest that implicit solvent dielectric functions must exclude interstitial high dielectric regions in order to yield physically meaningful results.
Swanson
Jessica M J
JM
Mongan
John
J
McCammon
J Andrew
JA
D004583:Electrons; D006639:Histidine / Q000737:chemistry; D008956:Models, Chemical; D012996:Solutions; D012997:Solvents / Q000737:chemistry*; D055672:Static Electricity
D012996:Solutions; D012997:Solvents; D006639:Histidine