Revised self-consistent continuum solvation in electronic-structure calculations

Details Revised self-consistent continuum solvation in electronic-structure calculations Revised self-consistent continuum solvation in electronic-structure calculations

2011-12-22

arxiv.org/abs/1112.5332v1

Physics

Chemical Physics

The following article has been accepted by The Journal of Chemical Physics. After it is published, it will be found at http:

Scientific paper

The solvation model proposed by Fattebert and Gygi [Journal of Computational Chemistry 23, 662 (2002)] and Scherlis et al. [Journal of Chemical Physics 124, 074103 (2006)] is reformulated, overcoming some of the numerical limitations encountered and extending its range of applicability. We first recast the problem in terms of induced polarization charges that act as a direct mapping of the self-consistent continuum dielectric; this allows to define a functional form for the dielectric that is well behaved both in the high-density region of the nuclear charges and in the low-density region where the electronic wavefunctions decay into the solvent. Second, we outline an iterative procedure to solve the Poisson equation for the quantum fragment embedded in the solvent that does not require multi-grid algorithms, is trivially parallel, and can be applied to any Bravais crystallographic system. Last, we capture some of the non-electrostatic or cavitation terms via a combined use of the quantum volume and quantum surface [Physical Review Letters 94, 145501 (2005)] of the solute. The resulting self-consistent continuum solvation (SCCS) model provides a very effective and compact fit of computational and experimental data, whereby the static dielectric constant of the solvent and one parameter allow to fit the electrostatic energy provided by the PCM model with a mean absolute error of 0.3 kcal/mol on a set of 240 neutral solutes. Two parameters allow to fit experimental solvation energies on the same set with a mean absolute error of 1.3 kcal/mol. A detailed analysis of these results, broken down along different classes of chemical compounds, shows that several classes of organic compounds display very high accuracy, with solvation energies in error of 0.3-0.4 kcal/mol, whereby larger discrepancies are mostly limited to self-dissociating species and strong hydrogen-bond forming compounds.

Affiliated with

Also associated with

No associations

Rating

Revised self-consistent continuum solvation in electronic-structure calculations does not yet have a rating. At this time, there are no reviews or comments for this scientific paper.

If you have personal experience with Revised self-consistent continuum solvation in electronic-structure calculations, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Revised self-consistent continuum solvation in electronic-structure calculations will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFWR-SCP-O-307486