Revised self-consistent continuum solvation in electronic-structure calculations

Andreussi, Oliviero; Dabo, Ismaila; Marzari, Nicola

doi:doi:10.1063/1.3676407

Volume/Page
Keyword
DOI
Citation
Advanced

Volume: Page/Article:

Search Content Type

article doi:

Citation:

Accurate thermochemistry from a parameterized coupled-cluster singles and doubles model and a local pair natural orbital based implementation for applications to larger systems

We have recently introduced a parameterized coupled-cluster singles and doubles model (pCCSD(α, β)) that consists of a bivariate parameterization of the CCSD equations and is inspired by the coupled electron pair approximations. In our previous work, it was demonstrated that the pCCSD(−1, 1) method is an improvement over CCSD for the calculation of geometries, harmonic frequencies, and potential energy surfaces for single bond-breaking. In this paper, we find suitable pCCSD parameters for applic...

A neural network potential-energy surface for the water dimer based on environment-dependent atomic energies and charges

Understanding the unique properties of water still represents a significant challenge for theory and experiment. Computer simulations by molecular dynamics require a reliable description of the atomic interactions, and in recent decades countless water potentials have been reported in the literature. Still, most of these potentials contain significant approximations, for instance a frozen internal structure of the individual water monomers. Artificial neural networks (NNs) offer a promising way ...

The solvation model proposed by Fattebert and Gygi [J. Comput. Chem. 23, 662 (2002)10.1002/jcc.10069] and Scherlis et al. [J. Chem. Phys. 124, 074103 (2006)10.1063/1.2168456] 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 multigrid 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 [M. Cococcioni, F. Mauri, G. Ceder, and N. Marzari, Phys. Rev. Lett. 94, 145501 (2005)10.1103/PhysRevLett.94.145501] of the solute. The resulting self-consistent continuum solvation 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 polarizable continuum 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.

Article Outline

INTRODUCTION
PREVIOUS APPROACHES
PRESENT MODEL
1. Electrostatic energy
2. Kohn-Sham energy and potential
3. Forces
CHOICE OF DIELECTRIC FUNCTION
ITERATIVE VS MULTIGRID
ADDITIONAL SOLVATION TERMS
RESULTS
1. Numerical details
2. Parametrization
  1. Fitting of tunable parameters
  2. Errors vs functional groups
  3. Molecular dynamics simulations
CONCLUSIONS

RELATED DATABASES

To view database links for this article, you need to log in.

KEYWORDS and PACS

Keywords

hydrogen bonds, iterative methods, molecular electronic states, organic compounds, permittivity, Poisson equation, solvation, solvent effects, wave functions

PACS

31.15.xv

Molecular dynamics and other numerical methods
31.70.Dk

Environmental and solvent effects
33.15.Fm

Bond strengths, dissociation energies

ARTICLE DATA

Digital Object Identifier

http://dx.doi.org/10.1063/1.3676407

PUBLICATION DATA

ISSN

0021-9606 (print)

1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef

American Institute of Physics

Figures (18) Tables (1)

Access to article objects (figures, tables, multimedia) requires a subscription; log in to view available files.
(Access to supplementary files, where available, is free for this journal.)