A polarizable continuum approach for the study of heterogeneous dielectric environments

J Chem Phys. 2006 May 14;124(18):184103. doi: 10.1063/1.2188392.

Abstract

We present a computational method, exploiting some features of the polarizable continuum model (PCM) to describe heterogeneous media; it belongs to the family of electrostatic embedding mixed methods, such as the more common quantum-mechanical (QM)/molecular mechanics approaches, with the electrostatic long range effects accounted for by a polarized continuum instead of atomic point charges. Provided effective dielectric constants are determined for the various parts of the system, the method is much faster than its atomistic counterpart, and allows for high-level QM calculations on the fragment of interest, using all the highly efficient computational tools developed for homogeneous PCM. Two case studies (the calculation of the pKa of solvent exposed acidic residues in a model protein, and the calculation of the electron spin resonance spectrum of a typical spin probe partially embedded in a membrane) are analyzed in some detail, to illustrate the application of the method to complex systems.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Algorithms*
  • Cell Membrane / chemistry
  • Cell Membrane / metabolism
  • Computer Simulation
  • Electron Spin Resonance Spectroscopy
  • Free Radicals / chemistry*
  • Histidine / chemistry
  • Hydrogen-Ion Concentration
  • Models, Molecular*
  • Proteins / chemistry*
  • Protons
  • Quantum Theory
  • Static Electricity
  • Thermodynamics

Substances

  • Free Radicals
  • Proteins
  • Protons
  • Histidine