Dynamical discrete/continuum linear response shells theory of solvation: convergence test for NH4+ and OH- ions in water solution using DFT and DFTB methods

J Phys Chem B. 2010 Dec 9;114(48):15941-7. doi: 10.1021/jp110202e. Epub 2010 Nov 15.

Abstract

A new dynamical discrete/continuum solvation model was tested for NH(4)(+) and OH(-) ions in water solvent. The method is similar to continuum solvation models in a sense that the linear response approximation is used. However, different from pure continuum models, explicit solvent molecules are included in the inner shell, which allows adequate treatment of specific solute-solvent interactions present in the first solvation shell, the main drawback of continuum models. Molecular dynamics calculations coupled with SCC-DFTB method are used to generate the configurations of the solute in a box with 64 water molecules, while the interaction energies are calculated at the DFT level. We have tested the convergence of the method using a variable number of explicit water molecules and it was found that even a small number of waters (as low as 14) are able to produce converged values. Our results also point out that the Born model, often used for long-range correction, is not reliable and our method should be applied for more accurate calculations.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Hydroxides / chemistry*
  • Ions / chemistry
  • Molecular Dynamics Simulation*
  • Quantum Theory*
  • Quaternary Ammonium Compounds / chemistry*
  • Solutions
  • Thermodynamics
  • Water / chemistry*

Substances

  • Hydroxides
  • Ions
  • Quaternary Ammonium Compounds
  • Solutions
  • Water