Perspective: Chemical Information Encoded in Electron Density.

Published

Journal Article

In this perspective, we review the chemical information encoded in electron density and other ingredients used in semilocal functionals. This information is usually looked at from the functional point of view: the exchange density or the enhancement factor are discussed in terms of the reduced density gradient. However, what parts of a molecule do these 3D functions represent? We look at these quantities in real space, aiming to understand the electronic structure information they encode and provide an insight from the quantum chemical topology (QCT). Generalized gradient approximations (GGAs) provide information about the presence of chemical interactions, whereas meta-GGAs can differentiate between the different bonding types. By merging these two techniques, we show new insight into the failures of semilocal functionals owing to three main errors: fractional charges, fractional spins, and non-covalent interactions. We build on simple models. We also analyze the delocalization error in hydrogen chains, showing the ability of QCT to reveal the delocalization error introduced by semilocal functionals. Then, we show how the analysis of localization can help understand the fractional spin error in alkali atoms, and how it can be used to correct it. Finally, we show that the poor description of GGAs of isodesmic reactions in alkanes is due to 1,3-interactions.

Full Text

Duke Authors

Cited Authors

  • Contreras-García, J; Yang, W

Published Date

  • March 2018

Published In

Volume / Issue

  • 34 / 6

Start / End Page

  • 567 - 580

PubMed ID

  • 31080323

Pubmed Central ID

  • 31080323

International Standard Serial Number (ISSN)

  • 1000-6818

Digital Object Identifier (DOI)

  • 10.3866/PKU.WHXB201801261

Language

  • eng