A polarizable continuum approach for the study of heterogeneous dielectric environments.
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.
Iozzi
Maria Francesca
MF
Dipartimento di Chimica, Università Federico II, Complesso Monte S. Angelo, via Cintia, I-80126 Napoli, Italy.
Cossi
Maurizio
M
Improta
Roberto
R
Rega
Nadia
N
Barone
Vincenzo
V
D000465:Algorithms; D002462:Cell Membrane / Q000737:chemistry / Q000378:metabolism; D003198:Computer Simulation; D004578:Electron Spin Resonance Spectroscopy; D005609:Free Radicals / Q000737:chemistry*; D006639:Histidine / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D008958:Models, Molecular; D011506:Proteins / Q000737:chemistry*; D011522:Protons; D011789:Quantum Theory; D055672:Static Electricity; D013816:Thermodynamics
D005609:Free Radicals; D011506:Proteins; D011522:Protons; D006639:Histidine